WO2014051090A1 - Oxide catalyst, method for producing same, and method for producing unsaturated aldehyde, diolefin or unsaturated nitrile - Google Patents
Oxide catalyst, method for producing same, and method for producing unsaturated aldehyde, diolefin or unsaturated nitrile Download PDFInfo
- Publication number
- WO2014051090A1 WO2014051090A1 PCT/JP2013/076364 JP2013076364W WO2014051090A1 WO 2014051090 A1 WO2014051090 A1 WO 2014051090A1 JP 2013076364 W JP2013076364 W JP 2013076364W WO 2014051090 A1 WO2014051090 A1 WO 2014051090A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- oxide catalyst
- reaction
- raw material
- oxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 480
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 80
- 150000001993 dienes Chemical class 0.000 title claims abstract description 48
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 42
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 281
- 229910052742 iron Inorganic materials 0.000 claims abstract description 77
- 150000001336 alkenes Chemical class 0.000 claims abstract description 66
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 64
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000013078 crystal Substances 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 49
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011733 molybdenum Substances 0.000 claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 33
- 239000010941 cobalt Substances 0.000 claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 33
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 31
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 31
- 239000011591 potassium Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims description 287
- 239000002994 raw material Substances 0.000 claims description 190
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 187
- 239000007789 gas Substances 0.000 claims description 159
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 127
- 239000000203 mixture Substances 0.000 claims description 119
- 239000002002 slurry Substances 0.000 claims description 94
- 229910052760 oxygen Inorganic materials 0.000 claims description 92
- 239000001301 oxygen Substances 0.000 claims description 92
- 239000000377 silicon dioxide Substances 0.000 claims description 91
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 65
- 238000002441 X-ray diffraction Methods 0.000 claims description 63
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 62
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 60
- 238000007254 oxidation reaction Methods 0.000 claims description 51
- 230000003197 catalytic effect Effects 0.000 claims description 45
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 45
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 238000010304 firing Methods 0.000 claims description 44
- 229910001882 dioxygen Inorganic materials 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 125000004429 atom Chemical group 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 10
- 150000005673 monoalkenes Chemical class 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 3
- 230000009467 reduction Effects 0.000 abstract description 60
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000007423 decrease Effects 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 151
- 238000011156 evaluation Methods 0.000 description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 105
- 239000007788 liquid Substances 0.000 description 94
- 150000001299 aldehydes Chemical class 0.000 description 91
- 230000000052 comparative effect Effects 0.000 description 65
- 239000012018 catalyst precursor Substances 0.000 description 61
- 239000007921 spray Substances 0.000 description 61
- 239000000047 product Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 51
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 49
- 239000002245 particle Substances 0.000 description 48
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 40
- 238000005259 measurement Methods 0.000 description 39
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 38
- 239000011164 primary particle Substances 0.000 description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 35
- 229910017604 nitric acid Inorganic materials 0.000 description 35
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 32
- 229910004298 SiO 2 Inorganic materials 0.000 description 32
- 239000006185 dispersion Substances 0.000 description 31
- 238000000634 powder X-ray diffraction Methods 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 27
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 27
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 27
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 26
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 25
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 25
- 230000000694 effects Effects 0.000 description 25
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 22
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- 239000001307 helium Substances 0.000 description 19
- 229910052734 helium Inorganic materials 0.000 description 19
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 229910017299 Mo—O Inorganic materials 0.000 description 12
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- 239000012895 dilution Substances 0.000 description 10
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
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- 229910052684 Cerium Inorganic materials 0.000 description 8
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 8
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 7
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- 230000002194 synthesizing effect Effects 0.000 description 7
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 7
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
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Definitions
- the present invention relates to an oxide catalyst, a method for producing the same, and a method for producing an unsaturated aldehyde, a diolefin, and an unsaturated nitrile using the oxide catalyst.
- Patent Document 1 describes a catalyst that focuses on Mo, Bi, Ce, K, Fe, Co, Mg, Cs, and Rb as the metal constituting the catalyst.
- the method for producing an unsaturated aldehyde includes, for example, at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol as a raw material, and an unsaturated aldehyde such as acrolein or methacrolein as an intermediate. It is used in a method for producing a (meth) acrylate such as methyl acrylate or methyl methacrylate by a general esterification reaction. As a method for producing this (meth) acrylate, a method comprising two reaction steps called a direct meta method and a method comprising three reaction steps called a direct acid method are known.
- the direct acid method is a process for producing (meth) acrylate in three steps (see, for example, Non-Patent Document 1).
- a catalyst in the first oxidation step of the direct acid method, at least one starting material selected from the group consisting of propylene, isobutylene, and t-butyl alcohol and molecular oxygen are subjected to a gas phase catalytic oxidation reaction.
- an unsaturated aldehyde such as acrolein or methacrolein.
- the second oxidation step is a step of producing (meth) acrylic acid by subjecting the unsaturated aldehyde obtained in the first oxidation step and molecular oxygen to a gas phase catalytic oxidation reaction in the presence of a catalyst. It is.
- the final esterification step is a step in which the (meth) acrylic acid obtained in the second oxidation step is further esterified to obtain (meth) acrylate. In the case of esterification, when methanol etc. are used as alcohol, methyl acrylate or methyl methacrylate can be obtained.
- At least one selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol is subjected to a gas phase catalytic oxidation reaction between a raw material and a molecular oxygen-containing gas.
- the first reaction step for producing an unsaturated aldehyde such as acrolein or methacrolein the obtained unsaturated aldehyde, an alcohol such as methanol, and molecular oxygen are reacted to produce methyl acrylate or methacrylic acid all at once. It consists of two catalytic reaction steps of the second reaction step for producing a (meth) acrylate such as methyl.
- the reaction system in which such an oxide catalyst is used includes a fixed bed, a fluidized bed, and a moving bed.
- the fixed bed reaction method is widely used industrially taking advantage of the fact that the flow state of the raw material gas is close to the extrusion flow and the reaction yield can be increased.
- the fixed-bed reaction method has low heat conductivity, and is not suitable for exothermic or endothermic reactions that require heat removal or heating.
- intense exothermic reactions such as oxidation reactions cause the temperature to rise rapidly and become difficult to control.
- the reaction may run away.
- the catalyst is damaged by such a rapid temperature rise and deteriorates at an early stage.
- the fluidized bed reaction method is a reaction method suitable for the catalytic oxidation reaction of olefin and / or alcohol, which is a highly exothermic reaction.
- Patent Documents 2 and 3 disclose the use of a fixed bed catalyst. Preferred is described.
- the catalyst described in the document is described as being usable in any method of fixed bed, moving bed and fluidized bed, but other than fixed bed There is no specific description of the reaction method.
- naphtha pyrolysis is the main method for producing 1,3-butadiene and other diolefins, but in recent years, with the shift to petroleum alternative resources, demand for production by gas phase oxidation reaction has increased. ing.
- a method for producing a diolefin using a gas phase oxidation reaction in the presence of a catalyst, a monoolefin having 4 or more carbon atoms such as n-butene or isopentene and molecular oxygen are subjected to catalytic oxidative dehydrogenation reaction.
- a method of producing a conjugated diolefin such as 1,3-butadiene and isoprene corresponding to the monoolefin.
- Patent Document 4 describes an oxide catalyst containing Mo, Bi, Fe, Ce, Ni, Mg, and Rb as a catalyst for the oxidative dehydrogenation reaction of a monoolefin. ing.
- an unsaturated nitrile such as acrylonitrile or methacrylonitrile
- one or more selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol in the presence of a catalyst, molecular oxygen and A method of reacting ammonia with ammonia is known. This method is widely known as the “ammoxidation process” and is currently practiced on an industrial scale.
- Patent Document 5 discloses a catalyst in which other components are added in addition to molybdenum, bismuth, iron, cerium, and nickel.
- Patent Document 6 discloses a catalyst in which other components are added in addition to molybdenum, bismuth, iron, antimony, nickel, and chromium.
- the disorder phase is a disordered phase or a metastable structure.
- the Mo site has a structure in which Fe is randomly substituted. Yes, it is characterized in that Mo atoms and Fe atoms form the same oxygen tetrahedral structure.
- the composition of the order phase is the same as that of the disorder phase, but the structure is different and is an ordered phase or a stable structure, which is obtained by heat treatment at a higher temperature than the disorder phase.
- Form That is, Fe atoms form an oxygen tetrahedron, and Mo atoms form an oxygen tetrahedron separately from Fe atoms.
- Non-Patent Document 2 describes that the disorder phase of Bi 3 Fe 1 Mo 2 O 12 is formed at 450 ° C., but undergoes a phase transition to the order phase at a reaction temperature of 475 ° C.
- the Y site occupies Bi and other elements or lattice defects at random or with a certain probability distribution.
- the X site and the Y site form a plane square lattice having a length equal to the lattice constant in the A-axis and B-axis directions, respectively. It occupies positions shifted in the A-axis direction and the B-axis direction, respectively.
- layers in each AB plane are repeatedly overlapped with each other (A / 2, 0) and (0.B / 2).
- the oxygen tetrahedron around the X site is arranged while rotating by 90 degrees around the C axis around the encapsulated atoms.
- FIG. 3 shows an X-ray diffraction (XRD) of the disorder phase Bi 3 Fe 1 Mo 2 O 12 .
- XRD X-ray diffraction
- FIG. 2 is a monoclinic system with a distorted celite structure, and the lattice constant of the unit cell is the length of each side.
- the X1 site is Mo and other elements or lattice defects, and the X2 site is Fe. And other elements or lattice defects, and Y sites are occupied by Bi and other elements or lattice defects.
- the peak of the 18.30 ° ⁇ 0.05 ° (101) plane of the disorder phase Bi 3 Fe 1 Mo 2 O 12 was 18.15 ⁇ 0.
- the reason why the fixed bed reaction method is practically adopted is as follows.
- the inventor presumes as follows. Since the target product, unsaturated aldehyde, is very reactive, it is susceptible to combustion cracking in the reactor before reaching the reactor outlet in an atmosphere where oxygen is present at high temperature, and it is not suitable for unsaturated carboxylic acids and dioxides. Sequentially decomposes into carbon.
- the fluidized bed reaction method in which the product contacts the catalyst requires a concentrated layer in which most of the catalyst flows and a dilute layer that is a space for reducing the linear velocity for catalyst separation. It is.
- the residence time in the reactor after leaving the catalyst layer (concentrated layer) is 10 times longer than that of the fixed bed reactor.
- the present invention has been made in view of the above problems, and suppresses the reduction and degradation of the catalyst even in an industrial long-time operation, and the unsaturated aldehyde yield, diolefin yield, or unsaturated nitrile yield. It is an object of the present invention to provide an oxide catalyst having a small decrease in the temperature, a method for producing the same, and a method for producing an unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst.
- the disorder phase is thermally unstable, and it is considered that there is no merit that the catalyst used in the gas phase oxidation reaction performed at a high temperature has the disorder phase. It was.
- the present invention is as follows.
- An oxide catalyst used for producing an unsaturated aldehyde, diolefin, or unsaturated nitrile from an olefin and / or an alcohol the oxide catalyst satisfying the following (1) to (3): (1) Contains molybdenum, bismuth, iron, cobalt, and element A (except for potassium, cesium, and rubidium) having an ionic radius greater than 0.96 ⁇ .
- the atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ⁇ a ⁇ 5
- the atomic ratio b of the iron is 1.5 ⁇ b ⁇ 6
- the atomic ratio c of the element A is 1 ⁇ c ⁇ 5
- the atomic ratio d of cobalt is 1 ⁇ d ⁇ 8
- It includes a disorder phase composed of a crystal system containing the molybdenum, the bismuth, the iron, and the element A.
- the diffraction angles (2 ⁇ ) in X-ray diffraction are 18.30 ° ⁇ 0.2 °, 28.20 ° ⁇ 0.2 °, 33.65 ° ⁇ 0.2 °, and 46.15 ° ⁇ 0.2.
- the oxide catalyst according to [1] which is 2.0 or more.
- the oxide catalyst according to [1] or [2] which has a composition represented by the following composition formula (1).
- Mo 12 Bi a Fe b A c Co d B e C f O g (1)
- Mo molybdenum
- Bi bismuth
- Fe iron
- element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium)
- Co Is cobalt element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin
- element C is selected from the group consisting of potassium, cesium, and rubidium
- a to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ⁇ a ⁇ 5, and Fe atomic ratio b is 1.5 ⁇ b.
- the atomic ratio c of the element A is 1 ⁇ c ⁇ 5
- the atomic ratio d of Co is 1 ⁇ d ⁇ 8
- the atomic ratio e of the element B is 0 ⁇ e ⁇ 3
- the atomic ratio f of C is 0 ⁇ f ⁇ 2.
- the ratio of Fe / Co is 0.8 ⁇ b / d
- g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.
- the said baking process is a manufacturing method of an oxide catalyst which has a temperature rising process which heats up the said dry body gradually over 100 hours from 100 degreeC to 200 degreeC.
- the calcining step includes calcining at a temperature of 200 to 300 ° C. to obtain a calcined product, A main firing step of subjecting the obtained temporary fired body to a main firing at a temperature of 300 ° C. or higher to obtain a catalyst; The method for producing an oxide catalyst according to [5] or [6] above.
- Production of an unsaturated aldehyde comprising an unsaturated aldehyde production step of obtaining an unsaturated aldehyde by oxidizing an olefin and / or alcohol using the oxide catalyst according to any one of [1] to [4] above Method.
- the reaction temperature of the gas phase catalytic oxidation reaction is 400 to 500 ° C .;
- the oxygen concentration in the product gas flowing out of the fluidized bed reactor is 0.03 to 0.5% by volume, 10.
- a method for producing a diolefin comprising the step of producing a diolefin by oxidizing a monoolefin having 4 or more carbon atoms using the oxide catalyst according to any one of [1] to [4] above .
- an oxide catalyst that suppresses reduction deterioration of the catalyst even in industrial long-term operation and has a small decrease in unsaturated aldehyde yield, diolefin yield, or unsaturated nitrile yield, and a method for producing the same, And the manufacturing method of an unsaturated aldehyde, a diolefin, and an unsaturated nitrile using the said oxide catalyst can be provided.
- FIG. 1 It is a diagram showing the crystal structure of the disorder phase Bi 3 Fe 1 Mo 2 O 12 . It is a diagram showing the crystal structure of the order phase Bi 3 Fe 1 Mo 2 O 12 . is a diagram showing an X-ray diffraction of the disorder phase Bi 3 Fe 1 Mo 2 O 12 and order phase Bi 3 Fe 1 Mo 2 O 12 .
- (b) orderer phase Bi 3 Fe 1 Mo 2 O 12 The relationship between the disorder phase content and peak a and peak b is shown. It is a figure which shows the X-ray diffraction of the catalyst obtained by Example A1 and Comparative Example A3.
- the oxide catalyst according to the first embodiment is An oxide catalyst used in producing an unsaturated aldehyde or diolefin from an olefin and / or an alcohol, which satisfies the following (1) to (3); (1) Molybdenum (hereinafter also referred to as “Mo”), bismuth (hereinafter also referred to as “Bi”), iron (hereinafter also referred to as “Fe”), cobalt (hereinafter also referred to as “Co”).
- Mo Molybdenum
- Bi bismuth
- Fe iron
- Co cobalt
- the olefin that is a raw material used in producing an unsaturated aldehyde or diolefin is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, propylene and isobutylene are preferable.
- the alcohol used as a raw material for producing the unsaturated aldehyde or diolefin is not particularly limited, and examples thereof include propanol, isopropanol, butanol, isobutanol, and t-butyl alcohol. Of these, isobutanol and t-butyl alcohol are preferred.
- acrolein and acrylic acid can be produced.
- isobutylene, isobutanol, and t-butyl alcohol are used as raw materials, , Methacrolein and methacrylic acid can be produced.
- n-butene when used as a raw material, butadiene can be produced.
- the olefin and alcohol used as raw materials may contain water, nitrogen, and alkanes such as propane, butane, and isobutane.
- Olefins and / or alcohols may be used alone or in combination of two or more.
- the oxide catalyst according to the first embodiment contains molybdenum, bismuth, iron, cobalt, and an element A (except for potassium, cesium, and rubidium) having an ionic radius larger than 0.96 ⁇ . .
- the presence of Mo, Bi, and Fe is indispensable from the viewpoint of making each metal element complex in a bismoly (Bi—Mo) catalyst in which Bi and Mo together form an active species.
- the atomic ratio a of Bi to Mo12 atoms is 1 ⁇ a ⁇ 5. From the viewpoint of further increasing the selectivity of the unsaturated aldehyde and / or diolefin, the atomic ratio a is preferably 1 ⁇ a ⁇ 4, more preferably 1 ⁇ a ⁇ 3.
- Fe is an essential element for industrially synthesizing unsaturated aldehyde and / or diolefin, similar to Mo and Bi.
- the atomic ratio b of Fe to Mo12 atoms is 1.5 ⁇ b ⁇ 6, preferably 1.5 ⁇ b ⁇ 5, and more preferably 1. .5 ⁇ b ⁇ 4.
- Bi and Mo tend to form complex oxides such as Bi 2 Mo 3 O 12 and Bi 2 MoO 6 that are active species such as gas phase catalytic oxidation, ammoxidation, and oxidative dehydrogenation. Although the selectivity of the unsaturated aldehyde and diolefin of the catalyst which consists of these complex oxides is high, activity becomes low. On the other hand, Fe and Mo form a complex oxide such as Fe 2 Mo 3 O 12 . Catalysts composed of these composite oxides have low activity and selectivity. However, when Mo, Bi and Fe are appropriately combined, a ternary composite oxide containing a disorder phase Bi 3 Fe 1 Mo 2 O 12 having high activity and high selectivity for unsaturated aldehyde and diolefin. Is formed.
- the present inventors have an ionic radius larger than 0.96 ⁇ ⁇ excluding potassium, cesium and rubidium. It has been found that the heat resistance of the oxide catalyst is improved by incorporating element A (hereinafter, also simply referred to as “element A”) into the structure of the oxide catalyst. That is, it has been found that it is useful for improving the heat resistance that the oxide catalyst contains a disorder phase composed of a crystal system containing molybdenum, bismuth, iron, and element A.
- element A element A
- the element A is not particularly limited as long as it has an ionic radius larger than 0.96 ⁇ ⁇ , excluding potassium, cesium and rubidium. At least one element selected from the group consisting of lanthanoid elements, or a mixture thereof; at least one element selected from the group consisting of elements such as lead and yttrium, or a mixture thereof; and calcium, strontium, barium, etc. Examples thereof include at least one element selected from the group consisting of alkaline earth metals, or a mixture thereof.
- the atomic ratio c of the element A to Mo12 atoms is 1 ⁇ c ⁇ 5, preferably 1 ⁇ c ⁇ 4, and more preferably 1 ⁇ c ⁇ 3.
- a quaternary composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is formed.
- a quaternary complex oxide containing the disorder phase Bi 3-x La x Fe 1 Mo 2 O 12 is formed.
- Bi 3+ ionic radius is 0.96 ⁇
- La 3+ having a larger ionic radius
- An oxide catalyst having heat resistance and high activity and selectivity can be obtained.
- a ternary composite oxide without La 3+ it transitions to the order phase at a temperature of 500 ° C. or higher.
- La having a slightly larger ion radius than Bi is present, the phase transition to the order phase is suppressed And the disorder phase structure is maintained.
- the element that exhibits the effect of suppressing the phase transition to the order phase is not limited to La, and the same effect is exhibited if it is element A listed above.
- Co is indispensable for imparting reduction resistance to the oxide catalyst according to the first embodiment.
- divalent iron is taken into CoMoO 4 to form a ternary crystal structure of Co 2+ -Fe 2+ -Mo-O. Since the incorporated iron has a metastable structure, it is easily oxidized in the reaction atmosphere and returns to trivalent. Therefore, it is presumed that redox turns during the reaction and suppresses reduction degradation.
- the atomic ratio d of Co to Mo12 atoms is 1 ⁇ d ⁇ 8, preferably 2 ⁇ d ⁇ 8, more preferably 2 ⁇ d ⁇ 6, and further preferably 3 ⁇ d ⁇ 5.
- a quaternary composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 tends to be difficult to form.
- the oxide catalyst according to the first embodiment preferably contains a quaternary composite oxide containing a disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 .
- X-ray diffraction X-ray diffraction
- the intensity (Ia) of the peak a at 2 ⁇ 33.65 ° ⁇ 0.2 ° and 2 ⁇
- the intensity ratio (Ia / Ib) between the intensity (Ib) of the peak b at 34.10 ° ⁇ 0.2 ° is preferably 2.0 or more, more preferably 2.5 or more, Preferably it is 3.0 or more.
- the intensity ratio (Ia / Ib) 1.1
- the intensity ratio (Ia / Ib) 3.3.
- the intensity ratio (Ia / Ib) is 2.0 or more, since a predetermined proportion of the disorder phase exists in the oxide catalyst, the yield of the unsaturated carboxylic acid is lowered, and the unsaturated aldehyde and / or diisocyanate. The olefin yield is improved.
- FIG. 4 shows the relationship between the content of the disorder phase and the peaks a and b.
- the mechanism of formation of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is not clear, but it is formed as an intermediate in the process of heat-treating the composite oxide of Bi and Mo. It is considered that a composite disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is formed by thermal diffusion of Fe and element A into the composite oxide to form a solid solution.
- the “single peak” should not be determined strictly, and can be determined as a single peak if the main peak detected at the diffraction angle is not split. That is, even if the peak has an inflection point, it can be regarded as a single peak. In addition, when there is a clearly small peak compared to the main peak, it is desirable to exclude the small peak and determine whether the main peak is single or split. “Small peak” refers to a peak having an intensity of less than 50% of the intensity of a main peak at a diffraction angle in a predetermined range.
- the “main peak” means the largest peak among the peaks existing within a predetermined range of diffraction angles. For example, when a maximum peak is detected at a position of 18.35 ° at a diffraction angle in the range of 18.30 ° ⁇ 0.2 °, the peak is defined as a main peak at 18.30 ° ⁇ 0.2 °. to decide.
- the oxide catalyst according to the first embodiment preferably has a composition represented by the following composition formula (1).
- the oxide catalyst has a composition represented by the following composition formula (1), generation of unsaturated carboxylic acid and carbon dioxide is suppressed, and the selectivity of unsaturated aldehyde and / or diolefin tends to be improved. .
- composition formula (1) Mo 12 Bi a Fe b A c Co d B e C f O g (1)
- Mo molybdenum
- Bi bismuth
- Fe iron
- element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium)
- Co Is cobalt element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin
- element C is selected from the group consisting of potassium, cesium, and rubidium
- a to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ⁇ a ⁇ 5, and Fe atomic ratio b is 1.5 ⁇ b.
- the atomic ratio c of the element A is 1 ⁇ c ⁇ 5
- the atomic ratio d of Co is 1 ⁇ d ⁇ 8
- the atomic ratio e of the element B is 0 ⁇ e ⁇ 3
- the atomic ratio f of C is 0 ⁇ f ⁇ 2.
- the ratio of Fe / Co is 0.8 ⁇ b / d
- g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.
- the element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and is substituted with some cobalt in the oxide catalyst. I guess that. From the viewpoint of maintaining a balance with the formation of a disordered phase crystal, the atomic ratio e of B is preferably 0 ⁇ e ⁇ 3, and more preferably 0 ⁇ e ⁇ 2.
- element B is not essential, it contributes to improving the activity of the catalyst or stabilizing the crystal structure of CoMoO 4 in the catalyst.
- copper has the effect of improving the activity of the catalyst
- nickel, magnesium, zinc and manganese have the effect of stabilizing the crystal structure of CoMoO 4 and suppressing phase transition due to pressure and temperature.
- Co is an essential element from the viewpoint of industrially synthesizing unsaturated aldehydes and / or diolefins similarly to Mo, Bi, and Fe.
- Co forms a composite oxide CoMoO 4 and serves as a carrier for highly dispersing active species such as Bi—Mo—O and a role of taking oxygen from the gas phase and supplying it to Bi—Mo—O and the like Fulfill.
- it is preferable to complex Co with Mo to form a complex oxide CoMoO 4 .
- the atomic ratio d of Co is preferably 1 ⁇ d ⁇ 8, more preferably 2 ⁇ d ⁇ 8, and even more preferably. 2 ⁇ d ⁇ 7, more preferably 2 ⁇ d ⁇ 5.
- the ratio of Fe / Co is preferably 0.8 ⁇ b / d, more preferably 0.8 ⁇ b / d ⁇ 1.5, and still more preferably 0.9 ⁇ b / d ⁇ 1. .2.
- the Fe / Co ratio is in the above range, single oxides such as Co 3 O 4 and CoO tend not to be generated.
- Element A is an element having an ionic radius larger than 0.96 mm, other than potassium, cesium and rubidium.
- the atomic ratio c of the element A is preferably 1 ⁇ c ⁇ 5, more preferably 1 ⁇ c ⁇ 4, and further preferably 1 ⁇ c ⁇ 3.
- the element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium.
- the element C is considered to show a role of neutralizing acid sites such as MoO 3 that have not been complexed in the oxide catalyst. Whether or not the element C is contained does not directly affect the crystal structure of the disorder phase described later.
- the atomic ratio f of element C to Mo12 atoms is preferably 0 ⁇ f ⁇ 2, more preferably 0.01 ⁇ f ⁇ 2, and further preferably 0.01 ⁇ f ⁇ 1 from the viewpoint of catalytic activity. It is. When the atomic ratio f is 0 or more, the neutralization effect tends to be further improved. In addition, when the atomic ratio f is 2 or less, the oxide catalyst tends to be basic to neutral, and the raw material olefin and alcohol are easily adsorbed to the oxide catalyst, and higher catalytic activity is expressed. Tend to.
- the metal component may contain an optional component that does not hinder the formation of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 .
- Element B and element C form a crystal structure separately from the crystal structure of the disorder phase described later, and therefore do not directly affect the crystal structure of the disorder phase.
- the oxide catalyst in the first embodiment may contain a carrier for supporting a metal oxide.
- a catalyst containing a support is preferable in terms of high dispersion of the metal oxide and high wear resistance of the supported metal oxide.
- the carrier when the catalyst is molded by an extrusion molding method, it is preferable to include a carrier.
- the carrier is not included. Also good.
- the carrier is not particularly limited, and examples thereof include at least one selected from the group consisting of silica, alumina, titania, and zirconia.
- the carrier is preferably silica.
- silica is more inert than other supports and can reduce selectivity for unsaturated aldehydes and / or diolefins, in addition to being able to impart suitable physical properties to fluidized bed reactions.
- the silica support is preferable in that it easily imparts high wear resistance to the supported metal oxide.
- Silica sol is suitable as the silica source.
- concentration of the silica sol in the raw material state in which other components are not mixed is preferably 10 to 50% by mass from the viewpoint of the dispersibility of the silica particles.
- the silica sol has 40 to 100% by mass of at least one silica sol (a) in which the average particle diameter of the silica primary particles is 20 to less than 55 nm, preferably 20 to 50 nm, It preferably contains 60 to 0% by mass of at least one silica sol (b) having an average particle diameter of silica primary particle diameter of 5 nm to less than 20 nm.
- the content of the carrier is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to 100% by mass of the total of the carrier and the oxide catalyst. And more preferably 5 to 10% by mass.
- the content of the carrier is within the above range, the yield of unsaturated aldehyde and / or diolefin tends to be further improved.
- the molding is performed by a known method such as tableting molding or extrusion molding.
- a known method such as tableting molding or extrusion molding.
- the shape at the time of molding include tablets, pellets, spheres, CDS (Computer Designed Shape), trilobes, wardrobes, rings, HGS (High Geometric Surface), clovers, and honeycombs.
- CDS and ring are preferable from the viewpoint of strength.
- the specific surface area of the oxide catalyst is preferably 2 to 5 m 2 / g, more preferably 2 to 4 m 2 / g.
- the specific surface area tends to be larger than 2 to 5 m 2 / g, but the specific surface area of the metal oxide containing no support alone is 2 to 5 m 2 / g. preferable.
- Bi is an essential element for the formation of active species together with Mo as called a bismoly (Bi-Mo) catalyst, so it is advantageous that it is contained in a large amount from the viewpoint of activity.
- Bi nitrate which is a Bi raw material conventionally used industrially, is a hardly water-soluble substance, and a large amount of nitric acid is required to dissolve Bi nitrate.
- the conventional catalyst preparation technique has a limit in increasing the Bi content. That is, a single oxide such as Bi 2 O 3 is generated, a homogeneous catalyst cannot be obtained, and the yield of unsaturated aldehyde and / or diolefin is low.
- Fe is essential for industrially synthesizing unsaturated aldehydes and / or diolefins in the same manner as Mo and Bi from the viewpoint of increasing catalytic activity without reducing the selectivity of unsaturated aldehydes and / or diolefins. It has been reported for a long time to be an element. However, International Publication as reported in 95/35273 pamphlet, there is a tendency that by-products such as CO and CO 2 amount is much happens when the Fe is increased, the selection of the unsaturated aldehyde and / or diolefins Since the rate is lowered, a small amount of Fe is optimal.
- the inventors of the present invention suppressed the generation of the order phase by a method for producing an oxide catalyst, which will be described later, and the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 It has been found that crystals are easily formed.
- the manufacturing method of the oxide catalyst in the first embodiment is as follows: A mixing step of mixing a raw material constituting a catalyst containing molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius larger than 0.96 ⁇ ⁇ ⁇ (excluding potassium, cesium, and rubidium) to obtain a raw slurry , A drying step of drying the obtained raw material slurry to obtain a dried product, A firing step of firing the obtained dried body; Have The firing step includes a temperature raising step of gradually raising the temperature of the dried body from 100 ° C. to 200 ° C. over 1 hour or more.
- the mixing step includes molybdenum, bismuth, iron, cobalt, and each metal element that constitutes the catalyst, including element A (excluding potassium, cesium, and rubidium) having an ionic radius greater than 0.96 ⁇ .
- This is a step of mixing the catalyst raw materials to obtain a raw material slurry.
- Molybdenum, bismuth, iron, cobalt, element A, rubidium, cesium, potassium, magnesium, copper, nickel, chromium, manganese, lead, alkaline earth metals, and rare earth elements are soluble in water or nitric acid. Examples thereof include ammonium salts, nitrates, hydrochlorides, organic acid salts, oxides, hydroxides, and carbonates.
- the oxides are preferably used as a dispersion in which the oxide is dispersed in water or an organic solvent, and more preferably used as an oxide dispersion in which the oxide is dispersed in water.
- a dispersion stabilizer such as a polymer may be included to disperse the oxide.
- the particle diameter of the oxide is preferably 1 to 500 nm, more preferably 10 to 80 nm.
- water-soluble polymers such as polyethylene glycol, methylcellulose, polyvinyl alcohol, polyacrylic acid, and polyacrylamide in the raw slurry; amines, aminocarboxylic acids, oxalic acid, malon A polyvalent carboxylic acid such as acid and succinic acid; and / or an organic acid such as glycolic acid, malic acid, tartaric acid, and citric acid can be appropriately added.
- the addition amount of the water-soluble polymer and / or organic acid is not particularly limited, but is preferably 30% by mass or less with respect to 100% by mass of the catalyst raw material from the viewpoint of the balance between uniformity and production amount.
- the method for preparing the raw slurry is not particularly limited as long as it is a commonly used method.
- a solution in which an ammonium salt of molybdenum is dissolved in warm water, and metal components other than molybdenum such as bismuth, iron, cobalt, and element A can be prepared by mixing a solution in which the salt is dissolved in water as a nitrate or a solution in which it is dissolved in an aqueous nitric acid solution.
- silica sol or the like may be added before and after mixing a solution in which molybdenum ammonium salt is dissolved in warm water and a solution in which metal components other than molybdenum are dissolved in water or an aqueous nitric acid solution. it can.
- concentration of metal elements in the raw material slurry after mixing is usually 1 to 50% by mass, preferably 10 to 40% by mass, with respect to 100% by mass of the raw material slurry, from the viewpoint of balance between uniformity and production amount. More preferably, it is 20 to 40% by mass.
- the above-mentioned raw material slurry preparation process is an example and is not limited.
- the addition procedure of each element source is changed, the pH of the raw material slurry is adjusted by adjusting the concentration of nitric acid or adding aqueous ammonia to the raw material slurry.
- the viscosity may be modified.
- the pH of the raw slurry is preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.
- the pH of the raw slurry is 8.0 or less, it is possible to suppress the formation of bismuth compound precipitation, and the tendency to further promote the generation of the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 It is in.
- a drying process is a process of drying the raw material slurry obtained at the mixing process, and obtaining a dry body.
- the drying method is not particularly limited and can be carried out by a commonly used method, and examples thereof include an arbitrary method such as evaporation to dryness, spray drying, and reduced pressure drying. Although it does not specifically limit as a spray-drying method, For example, methods, such as a centrifugal system, a two-fluid nozzle system, a high pressure nozzle system, etc. which are usually implemented industrially, are mentioned.
- the drying heat source at this time, it is preferable to use air heated by steam, an electric heater or the like.
- the temperature at the inlet of the dryer of the spray dryer is usually 150 to 400 ° C., preferably 180 to 400 ° C., more preferably 200 to 350 ° C.
- the firing step is a step of firing the dried body obtained in the drying step. Firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace.
- the firing step has a temperature raising step of gradually raising the temperature of the dried body from 100 to 200 ° C. over 1 hour or more. Through this heating process, the four components of Bi, Mo, Fe and element A are uniformly mixed at the atomic level, and the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is generated. It becomes easy.
- “gradual increase in temperature” means that the temperature is increased to a set temperature usually over 1 h to 10 h as a temperature increase time. The heating rate need not always be constant.
- the temperature raising time is usually 1h to 10h, preferably 1h to 5h, more preferably 2h to 4h.
- the method for firing the dried body varies depending on the raw material used. For example, when nitrate material is included in the raw material, it is preferable to carry out by two-stage baking of temporary baking and main baking. Specifically, a temporary firing step for obtaining a temporary fired body by pre-baking at a temperature of 200 to 300 ° C., and a main firing step for obtaining a catalyst by subjecting the obtained temporary fired body to a temperature of 300 ° C. or higher. are preferably performed.
- the temperature raising step is performed before the preliminary firing step, and then the temperature is raised to a temperature range of 200 ° C. to 300 ° C. usually over 1 h.
- the preliminary baking step baking is performed at a temperature range of 200 ° C to 300 ° C.
- the pre-baking time is usually 1h to 10h, preferably 2h to 8h, more preferably 3h to 6h.
- the purpose of calcination is to gradually burn nitric acid remaining in the dried body.
- the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 tends to be formed uniformly.
- provisional firing is performed in the temperature range of 200 ° C. to 300 ° C.
- the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is It becomes difficult to produce, and there is a risk that an order phase, a two-component oxide such as Fe 2 Mo 3 O 12 , Bi 2 Mo 3 O 12 , or A 2 Mo 3 O 12 may be produced.
- the second-stage main baking is performed using the obtained temporary baking body.
- the temperature of the main baking is higher than the temperature of the preliminary baking, preferably 300 ° C. or higher, more preferably 300 ° C. or higher and 700 ° C. or lower, further preferably 300 to 650 ° C., and still more preferably 400 ° C. to It is 600 ° C., particularly preferably 450 ° C. to 600 ° C.
- the main calcination temperature is in the above range, the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 tends to be more easily generated.
- the main baking time is usually 0.1 to 72 hours, preferably 2 to 48 from the viewpoint of promoting the formation of crystals by appropriately setting the product of the baking temperature and the baking time. Time, more preferably 3 to 24 hours.
- the firing time is preferably 24 to 72 hours, for example.
- the firing time is preferably 3 hours or less from the viewpoint of preventing the formation of the order phase.
- the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is generated in the main calcination step. .
- Methacrolein can be obtained, for example, by performing a gas phase catalytic oxidation reaction of isobutylene, isobutanol, and t-butyl alcohol using the oxide catalyst according to the first embodiment. it can.
- the molecular oxygen concentration is 1 to 20% by volume with respect to 1 to 10% by volume of isobutylene, isobutanol, t-butyl alcohol, or a mixed gas thereof in the presence of an oxide catalyst.
- the raw material gas to which the molecular oxygen-containing gas and the dilution gas are added can be introduced into the catalyst layer in the fixed bed reactor.
- the reaction temperature can be 250 to 480 ° C.
- the reaction pressure can be normal pressure to 5 atmospheres
- the space velocity can be 400 to 4000 / hr (under normal temperature pressure (NTP) conditions).
- NTP normal temperature pressure
- the molar ratio of oxygen to isobutylene, isobutanol, t-butyl alcohol, or mixed gas improves the yield of unsaturated aldehydes.
- it is usually 1.0 to 2.0, preferably 1.1 to 1.8, more preferably 1.2 to 1.8. .
- the molecular oxygen-containing gas is not particularly limited, for example, pure oxygen gas, N 2 O, and include a gas containing oxygen such as air. Among these, air is preferable from an industrial viewpoint.
- the diluent gas is not particularly limited, and examples thereof include nitrogen, carbon dioxide, water vapor, and a mixed gas thereof.
- the mixing ratio of the molecular oxygen-containing gas and the dilution gas is preferably 0.01 ⁇ molecular oxygen / (molecular oxygen-containing gas + dilution gas) ⁇ 0.3 in volume ratio. Further, the molecular oxygen content is preferably 1 to 20% by volume with respect to 100% by volume of the source gas.
- the water vapor in the raw material gas is effective in preventing coking of the catalyst, it is preferable to reduce the water vapor concentration in the diluting gas as much as possible in order to suppress by-production of carboxylic acids such as methacrylic acid and acetic acid.
- the water vapor content is usually 0 to 30% by volume with respect to 100% by volume of the source gas.
- Acrolein production method There are no particular restrictions on the conditions for producing acrolein by vapor phase catalytic oxidation of propylene, and the method is generally used when producing acrolein by vapor phase catalytic oxidation of propylene. Can do. For example, a mixed gas containing 1 to 15% by volume of propylene, 3 to 30% by volume of molecular oxygen, 0 to 60% by volume of water vapor, and 20 to 80% by volume of an inert gas such as nitrogen and carbon dioxide is reacted.
- the catalyst may be introduced at a space velocity (SV) of 300 to 5000 hr ⁇ 1 under a pressure of 250 to 450 ° C. and a pressure of 0.1 to 1 MPa.
- SV space velocity
- a reactor a general fixed bed reactor, a fluidized bed reactor, or a moving bed reactor can be used.
- the diolefin production method according to the first embodiment is obtained by oxidizing a monoolefin having 4 or more carbon atoms using the oxide catalyst according to the first embodiment. Having a diolefin production process. More specifically, in the diolefin production process, a diolefin is produced by subjecting a monoolefin having 4 or more carbon atoms and an oxygen source to a gas phase catalytic oxidation reaction in the presence of the oxide catalyst according to the first embodiment. It is the process of obtaining.
- the mixed gas of molecular oxygen containing gas and dilution gas can be used.
- the monoolefin having 4 or more carbon atoms is not particularly limited, and examples thereof include n-butene.
- the diolefin obtained varies depending on the monoolefin having 4 or more carbon atoms to be used. For example, when n-butene is used, butadiene is obtained.
- the molecular oxygen-containing gas is not particularly limited, and examples thereof include pure oxygen gas and gas containing oxygen such as air. Among these, it is preferable to use air as the molecular oxygen-containing gas. By using air, it tends to be more excellent from an industrial viewpoint such as cost.
- the diluent gas is not particularly limited, and examples thereof include nitrogen, carbon dioxide, water vapor, and a gas obtained by mixing two or more of these.
- the source gas supplied to the diolefin production process is a molecular oxygen-containing gas and a dilution gas so that the molecular oxygen concentration is 1 to 20% by volume with respect to 1 to 10% by volume of monoolefin having 4 or more carbon atoms. It is preferable that these are added.
- the reactor is not particularly limited, and examples thereof include a fixed bed reactor.
- the reaction temperature is preferably 250 to 450 ° C.
- the reaction pressure is preferably atmospheric pressure to 5 atm
- the space velocity is preferably 400 to 4000 / hr (under normal temperature pressure (NTP) conditions). .
- the oxide catalyst according to the second embodiment (hereinafter also referred to as “ammoxidation catalyst”) will be described.
- the oxide catalyst according to the second embodiment is An oxide catalyst used in the production of an unsaturated nitrile from an olefin and / or an alcohol, which satisfies the following (1) to (3); (1) containing molybdenum, bismuth, iron, cobalt, and an element A (excluding potassium, cesium and rubidium) having an ionic radius larger than 0.96 ⁇ , (2)
- the atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ⁇ a ⁇ 5
- the atomic ratio b of the iron is 1.5 ⁇ b ⁇ 6
- the atomic ratio c of the element A is 1 ⁇ c ⁇ 5
- the atomic ratio d of cobalt is 1 ⁇ d ⁇ 8
- the olefin that is a raw material used in producing the unsaturated nitrile is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, propylene and isobutylene are preferable.
- the alcohol used as a raw material for producing the unsaturated nitrile is not particularly limited, and examples thereof include propanol, butanol, isobutanol, and t-butyl alcohol. Of these, isobutanol and t-butyl alcohol are preferred.
- acrylonitrile when propylene or propanol is used as a raw material, acrylonitrile can be produced, and when isobutylene, isobutanol or t-butyl alcohol is used as a raw material, methacrylonitrile is used. Can be manufactured.
- Olefins and / or alcohols may be used alone or in combination of two or more.
- the unsaturated nitrile is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile.
- the oxide catalyst according to the first embodiment contains molybdenum, bismuth, iron, cobalt, and an element A (excluding potassium, cesium, and rubidium) having an ionic radius greater than 0.96%.
- element A excluding potassium, cesium, and rubidium
- the presence of Mo, Bi, and Fe is indispensable from the viewpoint of making each metal element complex in a bismoly (Bi—Mo) catalyst in which Bi and Mo together form an active species.
- the atomic ratio a of Bi to Mo12 atoms is 1 ⁇ a ⁇ 5, preferably 1 ⁇ a ⁇ 4, and more preferably 2 ⁇ a ⁇ 4.
- the selectivity of unsaturated nitrile tends to be further improved.
- Fe is an essential element for industrially synthesizing unsaturated nitriles like Mo and Bi, but when the Fe content increases, Fe is increased. 2 O 3 is generated, and by-products such as CO and CO 2 tend to increase, and the selectivity of unsaturated nitrile decreases. Further, even if the Fe content is increased, Fe 2 O 3 may not be generated. At this time, however, a two-component complex oxide called Fe 2 Mo 3 O 12 is generated.
- the atomic ratio b of Fe to Mo12 atoms of the ammoxidation catalyst in the second embodiment is preferably 1.5 ⁇ b ⁇ 6, more preferably 2.0 ⁇ b ⁇ 5, Preferably, 3 ⁇ b ⁇ 5.
- Bi and Mo are easy to form complex oxides such as Bi 2 Mo 3 O 12 and Bi 2 MoO 6 which are active species of ammoxidation reaction, and the selectivity of unsaturated nitrile is high, but the activity is low. There is a tendency.
- Fe and Mo form a composite oxide such as Fe 2 Mo 3 O 12, but a catalyst composed of these composite oxides has low activity and selectivity.
- Mo, Bi, and Fe are combined, the order phase Bi 3 Fe 1 Mo 2 O 12 is formed.
- the ammoxidation reaction is carried out industrially for a long time using a catalyst containing this structure, the initial yield is increased.
- the present inventors presume the reason for this reduction deterioration as follows.
- the valence of iron contained in Bi 3 Fe 1 Mo 2 O 12 immediately after the start of the reaction is in a trivalent state, but redox is repeated during the reaction, and the iron is reduced to divalent, and the divalent iron and molybdenum are reduced.
- the composite oxide (FeMoO 4 ) is formed. Mo and Bi form MoO 2 , Bi 2 O 3 and metal Bi. The formation of these stable compounds stabilizes iron, and it is assumed that redox does not rotate during the reaction and causes reduction degradation.
- the present inventors have found that, in addition to the three components of Mo, Bi, and Fe, the ionic radius is larger than 0.96 mm. It has been found that by further incorporating element A into the structure of the oxide catalyst, the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is formed and the reduction resistance is improved.
- the quaternary complex oxide having this structure is not only highly active and has a high selectivity for unsaturated nitriles, but also a stable complex oxide of divalent iron and molybdenum that causes reduction degradation even during long-term operation ( It was found that FeMoO 4 ) did not form and had reduction resistance.
- the element A is not particularly limited as long as it is an element other than potassium, cesium, and rubidium as long as the ion radius is larger than 0.96 ⁇ .
- lanthanum, cerium, praseodymium, neodymium, samarium, Europium, Gadolini At least one element selected from the group consisting of lanthanum, terbium, dysprosium, calcium and lead, or a mixture thereof, more preferably at least selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, calcium and lead One element or a mixture thereof.
- the atomic ratio c of the element A to 12 atoms of molybdenum is 1 ⁇ c ⁇ 5, preferably 1 ⁇ d ⁇ 4, and more preferably 1.5 ⁇ d ⁇ 3.
- a quaternary composite oxide containing a composite disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is easily formed.
- a quaternary complex oxide containing the disorder phase Bi 3-x La x Fe 1 Mo 2 O 12 is formed.
- the ammoxidation catalyst according to the second embodiment preferably contains a quaternary composite oxide containing a disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 .
- X-ray diffraction X-ray diffraction
- the intensity ratio (Ia / Ib) is 2.0 or more, a predetermined proportion of the disorder phase is present in the oxide catalyst. The yield tends to be further improved.
- FIG. 4 shows the relationship between the content of the disorder phase and the peaks a and b.
- the mechanism of formation of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is not clear, but it is formed as an intermediate in the process of heat-treating the composite oxide of Bi and Mo. It is considered that a composite disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is formed by thermal diffusion of Fe and element A into the composite oxide to form a solid solution.
- single peak and “main peak” are the same as in the first embodiment.
- the ammoxidation catalyst according to the second embodiment preferably includes a metal oxide having a composition represented by the following composition formula (2).
- the ammoxidation catalyst contains a metal oxide having a composition represented by the following composition formula (2), the selectivity of unsaturated nitrile tends to be improved.
- Mo molybdenum
- Bi bismuth
- Fe iron
- element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium)
- Co Is cobalt element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin
- element C is selected from the group consisting of potassium, cesium, and rubidium
- a to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ⁇ a ⁇ 5, and Fe atomic ratio b is 1.5 ⁇ b.
- the atomic ratio c of the element A is 1 ⁇ c ⁇ 5
- the atomic ratio d of Co is 1 ⁇ d ⁇ 8
- the atomic ratio e of the element B is 0 ⁇ e ⁇ 3
- the atomic ratio f of C is 0 ⁇ f ⁇ 2.
- the ratio of Fe / Co is 0.8 ⁇ b / d
- g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.
- Co is an essential element from the viewpoint of industrially synthesizing unsaturated nitriles like Mo, Bi, and Fe.
- Co forms a composite oxide CoMoO 4 and serves as a carrier for highly dispersing active species such as Bi—Mo—O and a role of taking oxygen from the gas phase and supplying it to Bi—Mo—O and the like Fulfill.
- it is preferable to complex Co with Mo to form a complex oxide CoMoO 4 .
- the atomic ratio d of Co is preferably 1 ⁇ d ⁇ 8, more preferably 2 ⁇ d ⁇ 8, and even more preferably. 2 ⁇ d ⁇ 6, more preferably 2 ⁇ d ⁇ 4.
- B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, chromium, and manganese, and is assumed to be substituted with some cobalt in the oxide catalyst. Is done. From the viewpoint of keeping a balance with the formation of the disorder phase crystal, the atomic ratio e of B is preferably 0 ⁇ e ⁇ 3, and more preferably 0 ⁇ e ⁇ 2. Although the element represented by B is not essential, it tends to contribute to stabilization of the crystal structure of CoMoO 4 in the catalyst.
- Element A is an element having an ionic radius larger than 0.96 mm, other than potassium, cesium and rubidium.
- the atomic ratio c of the element A is preferably 1 ⁇ c ⁇ 5, more preferably 1 ⁇ c ⁇ 4, and further preferably 1 ⁇ c ⁇ 3.
- the element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium, and is considered to have a role of neutralizing acid points such as MoO 3 that have not been complexed in the ammoxidation catalyst. It is done. Whether or not it contains potassium, cesium and / or rubidium does not directly affect the crystal structure of the disorder phase described later.
- the atomic ratio f of element C to Mo12 atoms is preferably 0 ⁇ f ⁇ 2, more preferably 0.01 ⁇ f ⁇ 2, and further preferably 0.01 ⁇ f ⁇ 1 from the viewpoint of catalytic activity. It is. When the atomic ratio f is 0 or more, the neutralization effect tends to be further improved.
- the oxide catalyst tends to change from basic to neutral, and propylene, isobutylene, isobutanol and t-butyl alcohol as raw materials tend to be adsorbed on the oxide catalyst. Therefore, the catalytic activity tends to be further improved.
- the elements B and C form a crystal structure separately from the crystal structure of the disorder phase described later, the elements B and C do not directly affect the crystal structure of the disorder phase.
- the metal component may contain an optional component that does not inhibit the formation of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 .
- the ammoxidation catalyst in the second embodiment may contain a carrier for supporting the metal oxide.
- a catalyst containing a support is preferable in terms of high dispersion of the metal oxide and high wear resistance of the supported metal oxide.
- the carrier is not particularly limited, and examples thereof include at least one selected from the group consisting of silica, alumina, titania, and zirconia.
- the carrier is preferably silica.
- silica in addition to being capable of imparting suitable physical properties for fluidized bed reactions, is itself inert compared to other supports, and does not reduce the selectivity to unsaturated nitriles without reducing metal oxidation. It is a preferred carrier in that it has a good binding action on objects.
- the silica support is preferable in that it easily imparts high wear resistance to the supported metal oxide.
- Silica sol is suitable as the silica source.
- concentration of the silica sol in the raw material state in which other components are not mixed is preferably 10 to 50% by mass from the viewpoint of the dispersibility of the silica particles.
- the silica sol has 40 to 100% by mass of at least one silica sol (a) in which the average particle diameter of the silica primary particles is 20 to less than 55 nm, preferably 20 to 50 nm, It preferably contains 60 to 0% by mass of at least one silica sol (b) having an average particle diameter of silica primary particle diameter of 5 nm to less than 20 nm.
- the content of the carrier is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to 100% by mass of the total of the carrier and the oxide catalyst. It is. When the content of the carrier is within the above range, the yield of the unsaturated nitrile tends to be further improved.
- a method for producing an ammoxidation catalyst in the second embodiment of the present invention is as follows.
- the firing step includes a temperature raising step of gradually raising the temperature of the dried body from 100 ° C. to 200 ° C. over 1 hour or more.
- the details of the method for producing an ammoxidation catalyst according to the second embodiment are the same as those of the first embodiment.
- the method for producing an unsaturated nitrile according to the second embodiment uses an oxide catalyst according to the second embodiment and olefin and / or alcohol in a fluidized bed reactor. And an unsaturated nitrile production step of obtaining unsaturated nitrile by reacting molecular oxygen with ammonia.
- the olefin and / or alcohol is not particularly limited, and examples thereof include one or more selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.
- one or more selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol is reacted with molecular oxygen and ammonia to thereby react acrylonitrile or methacrylate. Ronitrile can be produced.
- the reaction is preferably carried out using a fluidized bed reactor.
- the raw materials propylene, isobutylene, isobutanol, t-butyl alcohol, and ammonia are not necessarily highly pure, and industrial grade ones can be used.
- the molecular oxygen source it is usually preferable to use air, but a gas whose oxygen concentration is increased by mixing oxygen with air can also be used.
- the composition of the raw material gas the molar ratio of ammonia and molecular oxygen [(propylene, isobutylene, isobutanol and t-butyl alcohol) / ammonia / molecular oxygen] to propylene, isobutylene, isobutanol and t-butyl alcohol is preferable. Is 1 / 0.8 to 1.4 / 1.4 to 2.4, more preferably 1 / 0.9 to 1.3 / 1.6 to 2.2.
- the reaction temperature is preferably 350 to 550 ° C., more preferably 400 to 500 ° C.
- the reaction pressure is preferably normal pressure to 0.3 MPa.
- the contact time between the raw material gas and the catalyst is preferably 0.5 to 20 sec ⁇ g / cc, more preferably 1 to 10 sec ⁇ g / cc.
- the olefin and / or the alcohol and an oxygen source are subjected to a gas phase catalytic oxidation reaction in the fluidized bed reactor, and the unsaturated aldehyde is contained from the fluidized bed reactor. It is preferable to have an outflow process for flowing out the product gas.
- the olefin and / or the alcohol is preferably at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.
- reaction temperature of the gas phase catalytic oxidation reaction is 400 to 500 ° C. It is preferable that the oxygen concentration in the product gas flowing out from the fluidized bed reactor is 0.03 to 0.5% by volume. This will be described in more detail below.
- the raw material olefin is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, one or more compounds selected from the group consisting of propylene and isobutylene are preferable. By using such an olefin, the yield of unsaturated aldehyde tends to be further improved.
- the raw material alcohol is not particularly limited, and examples thereof include propanol, butanol, isobutanol, t-butyl alcohol, and the like. Of these, one or more compounds selected from the group consisting of propanol, isobutanol and t-butyl alcohol are preferred. By using such alcohol, the yield of unsaturated aldehyde tends to be further improved.
- the lower limit of the concentration of olefin and / or alcohol introduced into the fluidized bed reactor is preferably 5.0% by volume or more of the total gas introduced into the fluidized bed reactor, more preferably 6.0% by volume or more, 7.0 A volume% or more is more preferable.
- the upper limit is preferably 10% by volume or less, more preferably 9.5% by volume or less, and still more preferably 9.0% by volume or less.
- the yield of unsaturated aldehyde tends to be further improved.
- acrolein can be produced.
- isobutylene, isobutanol, or t-butyl alcohol is used as a raw material, methacrolein can be produced.
- the olefin and alcohol may contain propane, butane, isobutane and the like as water, nitrogen, and alkane.
- an olefin and / or alcohol and an oxygen source are subjected to a gas phase catalytic oxidation reaction using an oxide catalyst to produce an unsaturated aldehyde.
- an oxygen source in this gaseous-phase contact reaction, for example, the mixed gas of molecular oxygen containing gas and dilution gas can be used.
- the molecular oxygen-containing gas is not particularly limited, and examples thereof include pure oxygen gas and gas containing oxygen such as air. Among these, it is preferable to use air as the molecular oxygen-containing gas. By using air, it tends to be more excellent from an industrial viewpoint such as cost.
- the diluent gas is not particularly limited, and examples thereof include nitrogen, carbon dioxide, water vapor, and a gas obtained by mixing two or more of these.
- the mixing ratio of the molecular oxygen-containing gas and the dilution gas in the mixed gas it is preferable that the following inequality condition is satisfied by the volume ratio. 0.01 ⁇ molecular oxygen-containing gas / (molecular oxygen-containing gas + dilution gas) ⁇ 0.3
- the oxygen source supplied to the oxide catalyst is larger than that of olefin and / or alcohol.
- the oxygen source is preferably supplied at an appropriate ratio.
- the oxygen source is supplied so that the molar ratio of air to the catalyst layer and olefin and / or alcohol is 7.0 to 10.5. It is more preferable to supply so that it may become 8.0-9.5, and it is still more preferable to supply so that it may become 8.0-9.0.
- the molar ratio of air supplied to the catalyst layer is 7.0 or more with respect to the olefin and / or alcohol, the concentration of the olefin and / or alcohol is lowered, and the reduction deterioration of the oxide catalyst tends to be further suppressed.
- the molar ratio of the air supplied to the catalyst layer is 10.5 or less, the oxygen concentration supplied to the catalyst layer becomes low, and the oxidation deterioration of the oxide catalyst tends to be further suppressed.
- the olefin, alcohol, and molecular oxygen-containing gas may contain water vapor. By containing water vapor, coking to the oxide catalyst tends to be further prevented.
- the dilution gas may contain water vapor. It is preferable that the content of water vapor in the dilution gas is low. By including water vapor, the generation of by-products such as acetic acid tends to be further suppressed.
- the water vapor contained in the entire gas supplied to the reactor is preferably 0.01 to 30% by volume.
- the method for producing an unsaturated aldehyde according to the third embodiment preferably uses a fluidized bed reactor (hereinafter also simply referred to as “reactor”).
- the fluidized bed reactor is an apparatus having a structure in which a gas disperser, an interpolator, and a cyclone are included as main components in the reactor, and an oxide catalyst is made to flow while contacting with a raw material gas.
- a fluidized bed reactor described in a fluidized bed handbook published by Baifukan Co., Ltd., 1999
- a fluidized bed reactor of a bubble fluidized bed type is particularly suitable.
- the generated heat of reaction can be removed by using a cooling pipe inserted in the fluidized bed reactor.
- reaction temperature of gas phase catalytic oxidation reaction is preferably 400 to 500 ° C., more preferably 420 to 470 ° C., and further preferably 430 to 450. ° C.
- the reaction temperature is 400 ° C. or higher, the conversion rate and reaction rate are further improved, and the yield of unsaturated aldehyde tends to be further improved.
- the reaction temperature is 500 ° C. or lower, combustion decomposition of the generated unsaturated aldehyde tends to be further suppressed.
- the reaction temperature of the gas phase catalytic oxidation reaction can be measured with a thermometer inserted in the fluidized bed reactor.
- the gas phase contact reaction is an exothermic reaction
- the reaction temperature can be adjusted to the above range by removing the heat of reaction using a cooling pipe or supplying heat using a heating device.
- the method of introducing the olefin and / or alcohol and the oxygen source is not particularly limited.
- the gas containing the olefin and / or alcohol and the air or oxygen concentration are increased to the fluidized bed reactor filled with the oxide catalyst. Gases may be mixed and introduced in advance, or each gas may be introduced independently.
- the gas used for the reaction can be heated to a predetermined reaction temperature after being introduced into the reactor, or can be preheated and introduced into the reactor. Among these, in order to continuously and efficiently react, it is preferable to preheat and introduce into the reactor.
- the oxygen concentration in the product gas flowing out from the fluidized bed reactor is preferably 0.03 to 0.5% by volume, more preferably 0.03 to 0.2% by volume, and even more preferably 0.05. ⁇ 0.1% by volume.
- the reactor outlet oxygen concentration is 0.5% by volume or less, excessive reduction of the catalyst tends to be further suppressed.
- a catalyst is oxidized excessively by being 0.03 volume% or more, and it exists in the tendency which the yield of unsaturated aldehyde improves more in any case.
- the oxygen concentration in the product gas flowing out from the fluidized bed reactor is also referred to as “reactor outlet oxygen concentration”.
- the “reactor outlet oxygen concentration” refers to the oxygen concentration in the product gas containing an unsaturated aldehyde flowing out from the reactor outlet.
- the oxygen concentration at the outlet of the reactor can be measured within the range in which the ratio of oxygen in the product gas in the vicinity of the outlet of the fluidized bed reactor does not change. It doesn't have to be nearby. Therefore, the outlet oxygen concentration of the reactor may be measured in the gas from downstream of the reactor or immediately before flowing out of the reactor to immediately before being subjected to the purification operation.
- the product gas for measuring the reactor outlet oxygen concentration is sampled in a pipe between the reactor and the quenching tower provided downstream of the reactor. be able to.
- the oxygen concentration at the outlet of the reactor can be measured by gas chromatography equipped with a thermal conductivity detector (TCD).
- the oxygen concentration at the outlet of the reactor is the molar ratio of the oxygen source supplied to the fluidized bed reactor and the olefin and / or alcohol, the amount of gas containing oxygen supplied to the fluidized bed reactor, the reaction temperature, the pressure in the reactor, It can be adjusted by changing the contact time between the raw material mixed gas and the oxide catalyst, the catalyst amount, and the total gas amount supplied to the reactor. Especially, it is preferable to adjust by controlling the quantity of the molecular oxygen containing gas supplied to a fluidized bed reactor, for example, air.
- the reaction temperature is 440 ° C.
- the reaction pressure is 0.05 MPa
- the flow rate is 595 cm.
- the oxygen concentration in the reactor outlet gas can be changed from 0.4 vol% to 0.05 vol%.
- Conditions for adjusting the oxygen concentration at the outlet of the reactor include the amount of catalyst, contact time, reaction pressure, space velocity and the like as well as the conversion rate. By adjusting these conditions in combination, the oxygen concentration at the outlet of the reactor can be adjusted to an arbitrary value. For example, when the reaction is performed by adjusting the reaction temperature to 430 ° C. to 500 ° C. and the olefin and / or alcohol concentration to the range of 6 to 10% by volume, the following formula is used to adjust the reactor outlet oxygen concentration to the above range.
- the contact time is defined is preferably 5.0 (g ⁇ sec / cm 2 ) or less, 4.0 (g ⁇ sec / cm 2) , more preferably less, 3.0 (g ⁇ sec / cm 2) or less Further preferred.
- the reaction pressure is preferably from normal pressure to 5 atm.
- the space velocity is preferably 400 to 4000 / hr [under normal temperature pressure (NTP) conditions].
- the oxide catalyst used in the third embodiment is used.
- the presence / absence of each element in the oxide catalyst and the atomic ratio of each element can be identified by fluorescent X-ray elemental analysis (XRF).
- XRF fluorescent X-ray elemental analysis
- Mo, Bi, Fe, and Co are essential components for forming an oxide catalyst, and olefin and / or alcohol is oxidized by lattice oxygen in the oxide catalyst to produce an unsaturated aldehyde.
- lattice oxygen in the oxide catalyst is consumed in the oxidation reaction, oxygen vacancies are generated in the oxide catalyst, and as a result, the reduction of the oxide catalyst proceeds and proceeds as the oxidation reaction proceeds.
- the oxide catalyst is deactivated. Therefore, it is necessary to oxidize the reduced oxide catalyst quickly.
- Oxides containing Mo, Bi, Fe, and Co were consumed by dissociating and adsorbing molecular oxygen in the gas phase into the oxide in addition to the reactivity of the olefin and / or alcohol with the oxygen source.
- the reoxidation action for regenerating lattice oxygen is also excellent. Therefore, even when the oxidation reaction is performed for a long period of time, it is considered that the reoxidation action is maintained, and the oxide catalyst can be stably produced from the olefin and / or alcohol without deactivation.
- each metal element can be compounded.
- the atomic ratio a of Bi to Mo12 atoms is 1 ⁇ a ⁇ 5, preferably 1.5 ⁇ a ⁇ 4, more preferably 1.8 ⁇ a ⁇ . 4.
- Bi and Mo preferably form Bi—Mo—O composite oxides such as Bi 2 Mo 3 O 12 and Bi 2 MoO 6 which are active species such as gas phase catalytic oxidation and ammoxidation reaction.
- Fe is an essential element for industrially synthesizing unsaturated aldehydes, like Mo and Bi.
- the atomic ratio b of Fe to Mo12 atoms of the oxide catalyst is 1.5 ⁇ b ⁇ 6, preferably 2 ⁇ b ⁇ 5.5, more preferably 3 ⁇ b ⁇ 5.
- iron becomes a solid solution in CoMoO 4 and becomes a catalyst having reduction resistance even in a reactor having a small amount of oxygen.
- Co is an element indispensable for industrially synthesizing unsaturated aldehydes as described above, forms a complex oxide with Mo such as complex oxide CoMoO 4 , takes in oxygen from the gas phase, Bi— It is thought that it plays a role of supplying to Mo-O and the like.
- the atomic ratio d of Co is preferably 1 ⁇ d ⁇ 8, more preferably 2 ⁇ d ⁇ 7, and further preferably 2.5 ⁇ d ⁇ 6.
- the atomic ratio Fe / Co of iron and cobalt in the oxide catalyst used in the third embodiment is preferably Fe / Co ⁇ 0.8, more preferably Fe / Co ⁇ 1, and further preferably. Is Fe / Co ⁇ 1.05, more preferably Fe / Co ⁇ 1.1.
- the upper limit of Fe / Co is preferably 3 ⁇ Fe / Co, more preferably 2 ⁇ Fe / Co, and further preferably 1.5 ⁇ Fe / Co. Normally, iron becomes trivalent when oxidized. Trivalent iron is difficult to dissolve in CoMoO 4 , and it is difficult to obtain an oxide catalyst with high reduction resistance simply by increasing iron.
- the oxide catalyst used in the third embodiment preferably has a composition represented by the following formula (1).
- Mo 12 Bi a Fe b Co d A c B e C f O g (1) (Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt, A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium; B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, calcium, strontium, barium, tin, and lead; C represents at least one element selected from the group consisting of potassium, cesium, and rubidium; a to g represent atomic ratios of each element to 12 atoms of molybdenum, 1 ⁇ a ⁇ 5, 1.5 ⁇ b ⁇ 6, 1 ⁇ d ⁇ 6, Fe / Co ⁇ 1, 1 ⁇ c ⁇ 5, 0 ⁇ e ⁇ 3 and 0.
- A is a lanthanoid element and represents at least one element selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium.
- Bi and Mo described above form a Bi—Mo—O composite oxide, which has high catalytic activity but low melting point and low heat resistance.
- a lanthanoid element and Mo are difficult to form a composite oxide such as A—Mo—O, but have a high melting point and extremely high heat resistance.
- Bi, element A, and Mo are combined to form heat-resistant Bi-A-Mo-O, and combined with high activity and heat resistance suitable as a fluidized bed catalyst. Things are formed.
- B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, calcium, strontium, barium, tin, and lead. It is presumed that B substitutes for some cobalt in the oxide catalyst. Although the element represented by B is not essential, it contributes to improving the activity of the catalyst or stabilizing the crystal structure of CoMoO 4 in the catalyst. For example, copper has the effect of improving the activity of the catalyst, and nickel, magnesium, zinc and manganese have the effect of stabilizing the crystal structure of CoMoO 4 and suppressing phase transition due to pressure and temperature.
- Such an atomic ratio e of B is preferably 0 ⁇ e ⁇ 3, more preferably 0 ⁇ e ⁇ 2, and further preferably 0 ⁇ e ⁇ 1.5.
- e is in the above range, the effect can be exhibited without breaking the structure in which iron is dissolved in CoMoO 4 .
- C represents at least one element selected from the group consisting of cesium, rubidium and potassium.
- C is considered to show a role of neutralizing acid sites such as MoO 3 that have not been complexed in the oxide catalyst.
- the atomic ratio f of C to Mo12 atoms is preferably 0 ⁇ f ⁇ 2, more preferably 0.01 ⁇ f ⁇ 2, and further preferably 0.05 ⁇ f ⁇ 0.5. When f is within the above range, the catalytic activity tends to be further improved.
- the oxide catalyst is hardly made basic, and in the oxidation reaction of olefin and / or alcohol, the raw material olefin and / or alcohol is easily adsorbed to the oxide catalyst, and the catalyst There exists a tendency for activity to improve more.
- the oxide catalyst used in the third embodiment is supported on a carrier.
- the support is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass with respect to the total mass of the support and the oxide catalyst.
- a supported catalyst containing an oxide containing Mo, Bi, Fe, Co, and a lanthanoid atom is obtained by a known method, for example, a mixing step for preparing a raw slurry, a drying step for spray-drying the raw slurry, and a drying step.
- the obtained dried product can be obtained by a method including a firing step.
- the carrier is not particularly limited, but for example, at least one selected from the group consisting of silica, alumina, titania, and zirconia is preferable.
- the carrier is preferably silica.
- Silica is a carrier that is more inert than other carriers, in addition to the property that it can impart physical properties suitable for fluidized bed reactions, without reducing the activity and selectivity of the catalyst for the desired product, Has a good binding action with the catalyst.
- the oxide catalyst used in the third embodiment is not particularly limited, and can be produced by a known method.
- the oxide catalyst used in the third embodiment includes, for example, a mixing step of preparing a raw material slurry, a drying step of spray-drying the raw material slurry to obtain a dry body, and a baking step of firing the dry body.
- a mixing step of preparing a raw material slurry includes, for example, a drying step of spray-drying the raw material slurry to obtain a dry body, and a baking step of firing the dry body.
- a drying step of spray-drying the raw material slurry to obtain a dry body
- a baking step of firing the dry body can be obtained by:
- the preferable aspect of the manufacturing method of the oxide catalyst which has the said process is demonstrated.
- a raw material slurry is prepared using a catalyst raw material.
- the catalyst raw material include molybdenum, bismuth, iron, cobalt, and lanthanoid elements such as lanthanum, cerium, praseodymium, and neodymium.
- Other catalyst raw materials are not particularly limited, and examples include manganese, nickel, copper, zinc, lead, alkali metal elements, magnesium, calcium, strontium, barium, and other rare earth elements.
- These raw materials can be used as ammonium salts, nitrates, hydrochlorides, sulfates, and organic acid salts that are soluble in water or nitric acid.
- an ammonium salt is preferable as an element source of molybdenum.
- nitrate containing each element is preferable.
- silica, alumina, titania, zirconia, or the like can be used as an oxide carrier, but silica is preferably used as a carrier.
- Silica sol is preferred as the silica source.
- the preferred concentration of the silica sol in the state where other components such as raw material slurry are not mixed is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and further preferably 20 to 40% by mass. When the concentration is within the above range, the dispersibility of the silica particles tends to be more excellent.
- the silica sol is composed of at least one silica sol (a) having an average particle diameter of silica primary particles of 20 to 55 nm, preferably 20 to 50 nm, 40 to 100% by mass, silica 1 It is preferable to include 60 to 0% by mass of at least one silica sol (b) having an average particle diameter of 5 nm to 20 nm.
- the amount of the silica support carrying the resulting oxide catalyst is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably based on the total mass of the oxide catalyst and the silica support. Is 40 to 60% by mass.
- Preparation of the raw slurry can be performed by adding ammonium salt of molybdenum dissolved in water to silica sol, and then adding a solution in which nitrate of each element source other than molybdenum is dissolved in water or aqueous nitric acid solution. .
- the order of the above addition can be changed as appropriate.
- the raw material slurry obtained in the mixing step is spray-dried to obtain a dried body (dry particles).
- the atomization of the raw material slurry can be performed by a centrifugal method, a two-fluid nozzle method, a high-pressure nozzle method, or the like, which are usually carried out industrially. Among these, it is preferable to carry out by a centrifugal method.
- the particles obtained by spraying are dried.
- the drying heat source it is preferable to use air heated by steam, an electric heater or the like.
- the temperature at the dryer inlet is preferably 100 to 400 ° C, more preferably 150 to 300 ° C.
- the desired catalyst is obtained by firing the dried particles obtained in the drying step.
- the dried particles are preferably calcined at 150 to 400 ° C., if necessary, and then main calcining is performed at a temperature range of 400 to 700 ° C., preferably 500 to 700 ° C. for 1 to 20 hours.
- Firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace.
- the particle diameter of the catalyst is preferably distributed in the range of 10 to 150 ⁇ m.
- Example A will be described below to describe the first embodiment in more detail. However, the first embodiment is not limited to Example A described below.
- the atomic ratio of oxygen atoms in the oxide catalyst is determined by the valence conditions of other elements, and in the examples and comparative examples, the atomic ratio of oxygen atoms in the formulas representing the catalyst composition Omitted. Further, the composition ratio of each element in the oxide catalyst was calculated from the composition ratio of preparation.
- Examples A and Comparative Examples A below when an aqueous dispersion of various metals is used as a catalyst raw material, bismuth oxide, iron oxide, and cobalt oxide aqueous dispersions are obtained by oxidizing an aqueous dispersion manufactured by CIK Nanotech Co., Ltd. As the lanthanum and cerium oxide aqueous dispersion, an aqueous dispersion manufactured by Taki Chemical Co., Ltd. was used.
- Average particle diameter [nm] 6000 / (surface area [m 2 / g] ⁇ true density (8.99 g / cm 3 )
- XRD X-ray diffraction angle> XRD was measured by measuring the (111) plane and the (200) plane of the LaB 6 compound as defined by National Institute of Standards & Technology as the standard reference material 660. The respective values were 37.441 °, 43.506 ° It was standardized to become.
- Bruker D8 ADVANCE was used as the XRD device.
- the reduction evaluation was performed in order to accelerate the reduction resistance of the catalyst.
- the catalyst is reduced by the reduction treatment in the gas atmosphere not containing oxygen, and the catalyst is reoxidized by returning to the reaction evaluation condition. By repeating this, the reduction resistance of the accelerated catalyst can be evaluated.
- Example A the ionic radius of the element A used in Example A and Comparative Example A is as follows.
- Example A1 In a mixed solution of 90.5 g of ion-exchanged water and 127.5 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.5 g of molybdenum trioxide is stirred and mixed at about 70 ° C., dissolved, and dissolved (solution A). ) In addition, 204.75 g of 10% by mass bismuth oxide aqueous dispersion with an average particle size of 51 nm, 54.3 g of 15% by mass cobalt oxide aqueous dispersion with an average particle size of 22 nm, and 15% by mass of iron oxide water with an average particle size of 39 nm.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 520 ° C. for 6 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A2 67.5 g of ammonium heptamolybdate was dissolved in 202.6 g of warm water at about 90 ° C. (solution A). Also, 37.0 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.3 g of iron nitrate, 0.55 g of cesium nitrate, and 37.2 g of cobalt nitrate were dissolved in 41.9 g of 18% by mass nitric acid aqueous solution, 206.2 g of warm water was added (Liquid B).
- Both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 6 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A3 66.4 g of ammonium heptamolybdate was dissolved in 199.2 g of warm water at about 90 ° C. (solution A). Also, 47.0 g of bismuth nitrate, 13.5 g of cerium nitrate, 7.4 g of calcium nitrate, 42.8 g of iron nitrate, 1.56 g of rubidium nitrate, and 32.0 g of cobalt nitrate were dissolved in 41.5 g of 18% by mass nitric acid aqueous solution. 209.0 g of warm water at about 90 ° C. was added (Liquid B).
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 530 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A4 In a mixed solution of 90.6 g of ion-exchanged water and 127.6 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.5 g of molybdenum trioxide is added, stirred and mixed at about 70 ° C., dissolved, and dissolved (solution A).
- a solution (B) was prepared by mixing 50.4 g of an iron oxide aqueous dispersion with a diameter of 39 nm, 92.6 g of a 10% by mass lanthanum oxide aqueous dispersion with an average particle diameter of 40 nm, and 4.3 g of a 10% by mass cesium hydroxide liquid. Liquid).
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 520 ° C. for 6 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A5 69.1 g of ammonium heptamolybdate was dissolved in 207.2 g of warm water at about 90 ° C. (solution A). Also, 45.7 g of bismuth nitrate, 14.0 g of cerium nitrate, 2.3 g of manganese nitrate, 48.5 g of iron nitrate, 0.57 g of cesium nitrate, and 27.6 g of cobalt nitrate were dissolved in 40.9 g of 18% by mass nitric acid aqueous solution. Then, 195.4 g of warm water of about 90 ° C. was added (Liquid B).
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 5 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A6 70.4 g of ammonium heptamolybdate was dissolved in 21.2 g of warm water at about 90 ° C. (solution A). Also, 34.0 g of bismuth nitrate, 21.6 g of cerium nitrate, 35.0 g of iron nitrate, 0.58 g of cesium nitrate, and 44.8 g of cobalt nitrate were dissolved in 35.3 g of 18% by mass nitric acid aqueous solution. 140.8 g of warm water was added (Liquid B).
- Both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 6 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A7 64.4 g of ammonium heptamolybdate was dissolved in 193.1 g of warm water at about 90 ° C. (solution A). Also, 37.0 g of bismuth nitrate, 23.7 g of cerium nitrate, 36.9 g of iron nitrate, 0.41 g of cesium nitrate, and 54.3 g of cobalt nitrate were dissolved in 34.1 g of 18% by mass nitric acid aqueous solution. 128.7 g of warm water was added (Liquid B).
- Both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.2, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 5 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 530 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.3, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 520 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.5, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 460 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 530 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- a catalyst composition having a composition represented by Mo 12 Bi 1.6 Ce 0.4 Fe 1.0 Co 8.0 Cs 0.4 K 0.2 as an atomic ratio based on Mo12 atoms was prepared as follows. did. 364 g of ammonium heptamolybdate was dissolved in 1820 g of warm water at about 50 ° C. (solution A).
- the pseudo-spherical calcined catalyst composition precursor thus obtained was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and calcined at 460 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- divalent Fe was not dissolved in CoMoO 4 . This was considered because the atomic ratio Fe / Co of iron to cobalt does not satisfy Fe / Co ⁇ 1.
- Example A8 In a mixed solution of 90.7 g of ion-exchanged water and 127.8 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.6 g of molybdenum trioxide is stirred and mixed at about 70 ° C., dissolved and dissolved (solution A). ) Further, 205.3 g of an aqueous bismuth oxide dispersion having an average particle diameter of 51 nm of 10% by mass, 54.5 g of an aqueous cobalt oxide dispersion having an average particle diameter of 22 nm of 15% by mass, and iron oxide water having an average particle diameter of 39 nm of 15% by mass.
- a solution (liquid B) was obtained by mixing 57.2 g of the dispersion, 72.1 g of a 10% by mass lanthanum oxide aqueous dispersion having an average particle size of 40 nm, and 1.4 g of a 10% by mass cesium hydroxide solution.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 510 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Acrolein was synthesized from propylene using the obtained catalyst.
- 20 mL of catalyst is packed in a SUS jacketed reaction tube with an inner diameter of 15 mm, a source gas having a propylene concentration of 10% by volume, a water vapor concentration of 17% by volume and an air concentration of 73% by volume is passed through to conduct acrolein synthesis reaction at a reaction temperature of 320 ° C. Carried out.
- the reaction evaluation results are shown in Table 4.
- Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 250 ° C. in 20 minutes and held at 250 ° C. for 3 hours to obtain a provisional fired body.
- the obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 460 ° C. for 5 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
- Example A9 Using the same catalyst as Example A2, butadiene was synthesized from 1-butene as follows. A jacketed SUS reaction tube with a diameter of 14 mm was filled with 6.0 g of catalyst, and 120 mL of a mixed gas consisting of 1-butene 8% by volume, oxygen 12.8% by volume, nitrogen volume 79.2% at a reaction temperature of 360 ° C. Aeration was conducted at a flow rate of / min (NTP) to carry out a butadiene synthesis reaction. The reaction evaluation results are shown in Table 5.
- FIG. 5 shows X-ray diffraction peaks of the catalysts obtained in Example A1 and Comparative Example A3.
- Example A1 Regarding the peak of the 46.15 ° ⁇ 0.05 ° (204) plane of the catalyst obtained in Peak splitting was observed in Comparative Example catalyst obtained in A3 is 45.90 ° (640) plane and 46.46 ° (242) plane.
- Example B will be described below to describe the second embodiment in more detail. However, the second embodiment is not limited to Example B described below.
- the atomic ratio of oxygen atoms in the ammoxidation catalyst is determined by the valence conditions of other elements. In Examples and Comparative Examples, the atomic ratio of oxygen atoms in the formulas representing the composition of the catalyst is Omitted. Further, the composition ratio of each element in the ammoxidation catalyst was calculated from the composition ratio of preparation.
- Examples B and Comparative Examples B below when an aqueous dispersion of various metals is used as a catalyst raw material, bismuth oxide, iron oxide and cobalt oxide aqueous dispersions are obtained by oxidizing an aqueous dispersion manufactured by CIK Nanotech Co., Ltd. As the lanthanum and cerium oxide aqueous dispersion, an aqueous dispersion manufactured by Taki Chemical Co., Ltd. was used.
- Average particle diameter [nm] 6000 / (surface area [m 2 / g] ⁇ true density (8.99 g / cm 3 )
- XRD X-ray diffraction angle> XRD is measured by measuring the (111) plane and (200) plane of the LaB 6 compound as defined by National Institute of Standards & Technology as the standard reference material 660, and the respective values are 37.441 °, 43.506 °. It was standardized to become.
- Bruker D8 ADVANCE was used as the XRD apparatus.
- Conversion rate (number of moles of reacted raw material / number of moles of supplied raw material) ⁇ 100
- Selectivity (number of moles of compound produced / number of moles of reacted raw material) ⁇ 100
- Yield (Mole number of produced compound / Mole number of supplied raw material) ⁇ 100
- the raw material mixed gas flow rate (Ncc / sec) T is the reaction temperature (° C.), and P is the reaction pressure (MPa).
- the reduction evaluation was performed in order to accelerate the reduction resistance of the catalyst.
- the catalyst is reduced by the reduction treatment in the gas atmosphere not containing oxygen, and the catalyst is reoxidized by returning to the reaction evaluation condition. By repeating this, the reduction resistance of the accelerated catalyst can be evaluated.
- Reduction treatment by flowing 2 volume% of propylene, isobutylene, isobutanol and a mixed gas of t-butyl alcohol and helium 98 volume% at a temperature of 430 ° C. for 5 minutes at a flow rate of 3.64 cc (NTP conversion) per second. After that, it was returned to the above-mentioned reaction evaluation conditions and allowed to flow for 5 minutes. This was set as one set, and a total of 100 sets were carried out to evaluate the reaction. Furthermore, 100 sets were implemented, reaction evaluation was performed, and reduction resistance was evaluated.
- Example B the ionic radius of the element A used in Example B and Comparative Example B is as follows.
- Example B1 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 70.3 g of ammonium heptamolybdate was dissolved in 211.0 g of hot water at about 90 ° C. (solution A).
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B2 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 69.3 g of ammonium heptamolybdate was dissolved in 207.8 g of warm water at about 90 ° C. (solution A).
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B3 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 69.7 g of ammonium heptamolybdate was dissolved in 209.1 g of warm water at about 90 ° C. (solution A).
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 270 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B4 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 74.5 g of ammonium heptamolybdate was dissolved in 223.4 g of warm water at about 90 ° C. (solution A).
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 240 ° C. over 1 hour and held for 4 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 580 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B5 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 67.3 g of ammonium heptamolybdate was dissolved in 202.0 g of hot water at about 90 ° C. (solution A).
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B6 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 70.6 g of ammonium heptamolybdate was dissolved in 211.8 g of warm water at about 90 ° C. (solution A).
- an aqueous 18% by mass nitric acid solution containing 37.1 g of bismuth nitrate, 21.5 g of cerium nitrate, 41.5 g of iron nitrate, 0.63 g of rubidium nitrate, 10.2 g of magnesium nitrate, 19.5 g of cobalt nitrate and 9.8 g of nickel nitrate It was dissolved in 41.3 g, and 193.1 g of hot water at about 90 ° C. was added (Liquid B). The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C.
- a raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B7 125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass. 70.3 g of ammonium heptamolybdate was dissolved in 210.8 g of warm water at about 90 ° C. (solution A).
- a raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 4 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- the silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Table 6 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body.
- the obtained calcined product was calcined in the air at 580 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- Example B5 The same oxide catalyst precursor as in Example B1 was heated to 250 ° C. in air over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst.
- the composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
- As a catalyst reaction evaluation 55 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 5.8 (sec ⁇ g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
- Example B8 Using the catalyst of Example B1, as a reaction evaluation, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of isobutylene was performed at a contact time of 5.4 (sec ⁇ g / cc). . Table 9 shows the reaction evaluation results. Table 9 also shows the results of reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
- Comparative Example B6 Using the same catalyst as in Comparative Example B5, as a reaction evaluation, 55 g of catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of isobutylene was performed at a contact time of 6.0 (sec ⁇ g / cc). It was. Table 9 shows the reaction evaluation results. Table 9 also shows the results of reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
- Example C the third embodiment will be described in more detail with reference to Example C.
- the third embodiment is not limited to these Examples C.
- the atomic ratio of oxygen atoms in the oxide catalyst is determined by the valence conditions of the other elements.
- the oxygen atom atoms in the formulas representing the catalyst composition The ratio is omitted.
- the composition ratio of each element in the oxide catalyst was calculated from the composition ratio of preparation.
- Example C the conversion rate, selectivity, and yield used to represent the reaction results are defined by the following equations.
- the “number of moles of raw material” in the formula is the number of moles of olefin and / or alcohol.
- Example C1 125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
- the silica raw material, both liquid A and liquid B were mixed and stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 1 h, heated up to 250 ° C. over 2 h, and then held at 250 ° C. for 3 hours for pre-firing. Got the body.
- the obtained calcined product was calcined at 600 ° C. for 3 hours in the air to obtain an oxide catalyst.
- Table 10 shows the composition of the obtained oxide catalyst.
- the methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa.
- Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
- the methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa.
- Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
- Example C8 125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
- the silica raw material, both liquid A and liquid B were mixed and stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 1 h, heated up to 250 ° C. over 2 h, and then held at 250 ° C. for 3 hours for pre-firing. Got the body.
- the obtained calcined product was calcined in the air at 590 ° C. for 3 hours to obtain an oxide catalyst.
- the composition of the oxide catalyst is shown in Table 10.
- Example C9 125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
- the silica raw material, both liquid A and liquid B were mixed and stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 1 h, heated up to 250 ° C. over 2 h, and then held at 250 ° C. for 3 hours for pre-firing. Got the body.
- the obtained calcined product was calcined in the air at 580 ° C. for 3 hours to obtain an oxide catalyst.
- the composition of the oxide catalyst is shown in Table 10.
- the methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa.
- Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
- the silica raw material, both liquid A and liquid B were mixed and stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air to 250 ° C. over 2 hours, and then held at 250 ° C. for 3 hours to obtain a temporarily fired body.
- the obtained calcined product was calcined in the air at 570 ° C. for 2 hours to obtain an oxide catalyst.
- the composition of the oxide catalyst is shown in Table 10.
- the silica raw material, both liquid A and liquid B were mixed and stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry.
- This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor.
- the obtained oxide catalyst precursor was heated in air to 250 ° C. over 2 hours, and then held at 250 ° C. for 3 hours to obtain a temporarily fired body.
- the obtained calcined product was calcined at 600 ° C. for 3 hours in the air to obtain an oxide catalyst.
- Table 10 shows the composition of the obtained oxide catalyst.
- the peak due to the composite oxide containing Co, Mo and divalent Fe is not 26.46 °, but the shift value is ⁇ °. Presented at 26.46 ° - ⁇ ° (0 ⁇ ). If there is a peak in the range of 26.30 to 26.40, it is determined that a three-component crystal of Co 2+ —Fe 2+ —Mo—O was formed.
- XRD XRD is measured by measuring the (111) plane and the (200) plane of the LaB 6 compound as defined by National Institute of Standards & Technology as the standard reference material 660, and the measured values are 37.441 °, 43.43 °, respectively. It normalized so that it might become 506 degrees.
- Bruker D8 ADVANCE was used as the XRD measurement device.
- divalent Fe was dissolved in CoMoO 4 .
- the present invention has industrial applicability as an oxide catalyst used in the production of unsaturated aldehydes or diolefins from olefins and / or alcohols.
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Abstract
Description
非特許文献2に記載されたdisorder相Bi3Fe1Mo2O12の結晶構造を図1に示す。シーライト型結晶(CaWO4型)の正方晶系であり、単位胞の格子定数については、2本の長さは等しく、3本のそれぞれのなす角は90度である(A=B≠C、α=β=γ=90度)。また、酸素四面体で囲まれたXサイト、酸素で囲まれていないYサイトの2つのサイトを有し、XサイトにはMoとFeがランダム、又はある確率分布を持って占有している。Yサイトは、Bi及びその他元素若しくは格子欠陥がランダム又はある確率分布を持って占有している。AB面内の各層は、XサイトとYサイトが、それぞれA軸、B軸方向の格子定数と等しい長さの平面正方格子を作っており、互いに、面内で格子定数の1/2ずつ、A軸方向、B軸方向それぞれにずれた位置を占めている。C軸方向の積層は、各AB面内の層が、(A/2,0)、(0.B/2)それぞれずれることを繰り返し重なっている。積層の際、Xサイトの周りの酸素4面体は、内包する原子を中心にC軸の周りに90度ずつ回転しながら、配置される。 1) Disorder phase Bi 3 Fe 1 Mo 2 O 12
The crystal structure of the disorder phase Bi 3 Fe 1 Mo 2 O 12 described in Non-Patent Document 2 is shown in FIG. It is a tetragonal system of celite type crystal (CaWO 4 type), and the unit cell lattice constant is equal in length of two, and the angle formed by each of the three is 90 degrees (A = B ≠ C Α = β = γ = 90 degrees). In addition, there are two sites, an X site surrounded by an oxygen tetrahedron and a Y site not surrounded by oxygen, and Mo and Fe are occupied at the X site randomly or with a certain probability distribution. The Y site occupies Bi and other elements or lattice defects at random or with a certain probability distribution. In each layer in the AB plane, the X site and the Y site form a plane square lattice having a length equal to the lattice constant in the A-axis and B-axis directions, respectively. It occupies positions shifted in the A-axis direction and the B-axis direction, respectively. In the stacking in the C-axis direction, layers in each AB plane are repeatedly overlapped with each other (A / 2, 0) and (0.B / 2). At the time of stacking, the oxygen tetrahedron around the X site is arranged while rotating by 90 degrees around the C axis around the encapsulated atoms.
比較のため、order相Bi3Fe1Mo2O12の結晶構造を図2に示すが、歪んだシーライト構造の単斜晶系であり、単位胞の格子定数については、各辺の長さは、それぞれ異なる。3本の基本ベクトルのなす角は、2つが90度であり、1つが異なっている(A≠B≠C、α=γ=90度、β≠90度)。酸素四面体で囲まれた不等価な2つのサイト、X1、X2と、酸素で囲まれていないYサイトの3つのサイトを有し、X1サイトはMo及びその他元素又は格子欠陥、X2サイトはFe及びその他元素又は格子欠陥、YサイトはBi及びその他元素又は格子欠陥が占有している。 2) order phase Bi 3 Fe 1 Mo 2 O 12
For comparison, the crystal structure of the order phase Bi 3 Fe 1 Mo 2 O 12 is shown in FIG. 2, which is a monoclinic system with a distorted celite structure, and the lattice constant of the unit cell is the length of each side. Are different. Two of the angles formed by the three basic vectors are 90 degrees, and one is different (A ≠ B ≠ C, α = γ = 90 degrees, β ≠ 90 degrees). It has three non-equivalent sites surrounded by an oxygen tetrahedron, X1 and X2, and a Y site that is not surrounded by oxygen. The X1 site is Mo and other elements or lattice defects, and the X2 site is Fe. And other elements or lattice defects, and Y sites are occupied by Bi and other elements or lattice defects.
disorder相Bi3Fe1Mo2O12は、Xサイト若しくはYサイトがそれぞれ等価であるか、又は異種元素がランダムに配位している。一方、order相では、Xサイト若しくはYサイトは、異なる元素種又は欠陥が規則正しく、決まったサイトに占有し、2種類のサイトに区別される。このため、order相のX線回折ではピークが分裂するのに対し、disorder相では単一なピークが検出される(図3の矢印に示す)ことが特徴である。X線回折角2θ=10°~60°の範囲を測定すると、disorder相Bi3Fe1Mo2O12の18.30°±0.05°(101)面のピークが18.15±0.05°(310)面と18.50±0.05°(111)面にピーク分裂し、disorder相の28.20°±0.05°(112)面のピークが28.05°±0.05°(221)面と28.40°±0.05°(42-1)面にピーク分裂し、disorder相の33.65°±0.05°(200)面のピークが33.25°±0.05°(600)面と34.10±0.05°(202)面にピーク分裂し、disorder相の46.15°±0.05°(204)面のピークが45.85°±0.05°(640)面と46.50±0.05°(242)面にピーク分裂する。 3) Difference in structure between the disorder phase Bi 3 Fe 1 Mo 2 O 12 and the order phase Bi 3 Fe 1 Mo 2 O 12 , is the disorder phase Bi 3 Fe 1 Mo 2 O 12 equivalent to the X site or the Y site? Or different elements are coordinated randomly. On the other hand, in the order phase, the X site or Y site is classified into two types of sites, with different element types or defects regularly occupying a predetermined site. For this reason, the peak is split in the X-ray diffraction of the order phase, whereas a single peak is detected in the disorder phase (indicated by an arrow in FIG. 3). When the X-ray diffraction angle 2θ = 10 ° to 60 ° was measured, the peak of the 18.30 ° ± 0.05 ° (101) plane of the disorder phase Bi 3 Fe 1 Mo 2 O 12 was 18.15 ± 0. The peak splits into the 05 ° (310) plane and the 18.50 ± 0.05 ° (111) plane, and the peak of the 28.20 ° ± 0.05 ° (112) plane of the disorder phase is 28.05 ° ± 0. The peaks split into the 05 ° (221) plane and the 28.40 ° ± 0.05 ° (42-1) plane, and the peak of the 33.65 ° ± 0.05 ° (200) plane of the disorder phase was 33.25 °. The peaks split into ± 0.05 ° (600) plane and 34.10 ± 0.05 ° (202) plane, and the peak of 46.15 ° ± 0.05 ° (204) plane of the disorder phase is 45.85 °. Peaks at ± 0.05 ° (640) plane and 46.50 ± 0.05 ° (242) plane To crack.
〔1〕
オレフィン及び/又はアルコールから、不飽和アルデヒド、ジオレフィン、又は不飽和ニトリルを製造する際に用いられる酸化物触媒であって、下記(1)~(3)を満たす酸化物触媒;
(1)モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含有し、
(2)前記モリブデン12原子に対する、前記ビスマスの原子比aが1≦a≦5であり、前記鉄の原子比bが1.5≦b≦6であり、前記元素Aの原子比cが1≦c≦5であり、前記コバルトの原子比dが1≦d≦8であり、
(3)前記モリブデン、前記ビスマス、前記鉄、及び前記元素Aを含む結晶系からなるdisorder相を含む。
〔2〕
X線回折における回折角(2θ)が、18.30°±0.2°、28.20°±0.2°、33.65°±0.2°、及び46.15°±0.2°の範囲に単一ピークを有し、且つ、
2θ=33.65°±0.2°のピークaの強度(Ia)と、2θ=34.10°±0.2°のピークbの強度(Ib)との強度比(Ia/Ib)が2.0以上である、前項〔1〕に記載の酸化物触媒。
〔3〕
下記組成式(1)で表される組成を有する、前項〔1〕又は〔2〕に記載の酸化物触媒。
Mo12BiaFebAcCodBeCfOg (1)
(式中、Moはモリブデンであり、Biはビスマスであり、Feは鉄であり、元素Aはイオン半径が0.96Åよりも大きな元素(ただし、カリウム、セシウム及びルビジウムを除く)であり、Coはコバルトであり、元素Bはマグネシウム、亜鉛、銅、ニッケル、マンガン、クロム、及び錫からなる群より選ばれる少なくとも1種の元素であり、元素Cはカリウム、セシウム、及びルビジウムからなる群より選ばれる少なくとも1種の元素であり、a~gは、Mo12原子に対する各元素の原子比であり、Biの原子比aは1≦a≦5であり、Feの原子比bは1.5≦b≦6であり、元素Aの原子比cは1≦c≦5であり、Coの原子比dは1≦d≦8であり、元素Bの原子比eは0≦e<3であり、元素Cの原子比fは0≦f≦2であり、Fe/Coの比は0.8≦b/dであり、gは酸素以外の構成元素の原子価によって決まる酸素の原子数である。)
〔4〕
担体として、シリカ、アルミナ、チタニア、及びジルコニアからなる群より選ばれる少なくとも1種をさらに含む、前項〔1〕~〔3〕のいずれか1項に記載の酸化物触媒。
〔5〕
モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含む、触媒を構成する原料を混合して原料スラリーを得る混合工程と、
得られた該原料スラリーを乾燥して乾燥体を得る乾燥工程と、
得られた該乾燥体を焼成する焼成工程と、
を有し、
前記焼成工程は、前記乾燥体を100℃から200℃まで1時間以上掛けて徐々に昇温する昇温工程を有する、酸化物触媒の製造方法。
〔6〕
前記原料スラリーのpHが8以下である、前項〔5〕に記載の酸化物触媒の製造方法。
〔7〕
前記焼成工程は、200~300℃の温度で仮焼成して仮焼成体を得る仮焼成工程と、
得られた仮焼成体を300℃以上の温度で本焼成して触媒を得る本焼成工程と、
を有する、前項〔5〕又は〔6〕に記載の酸化物触媒の製造方法。
〔8〕
前項〔1〕~〔4〕のいずれか1項に記載の酸化物触媒を用いて、オレフィン及び/又はアルコールを酸化して不飽和アルデヒドを得る不飽和アルデヒド製造工程を有する、不飽和アルデヒドの製造方法。
〔9〕
前記オレフィン及び/又は前記アルコールが、プロピレン、イソブチレン、プロパノール、イソプロパノール、イソブタノール、及びt-ブチルアルコールからなる群より選ばれる少なくとも1種である、前項〔8〕に記載の不飽和アルデヒドの製造方法。
〔10〕
前記不飽和アルデヒド製造工程において、流動層反応器中で、前記オレフィン及び/又は前記アルコールと、酸素源と、を気相接触酸化反応させ、前記流動層反応器から前記不飽和アルデヒドを含む生成ガスを流出させる流出工程を有する、前項〔8〕又は〔9〕に記載の不飽和アルデヒドの製造方法。
〔11〕
前記気相接触酸化反応の反応温度が400~500℃であり、
前記流動層反応器から流出する前記生成ガス中の酸素濃度が0.03~0.5体積%である、
前項〔8〕~〔10〕のいずれか1項に記載の不飽和アルデヒドの製造方法。
〔12〕
前項〔1〕~〔4〕のいずれか1項に記載の酸化物触媒を用いて、炭素数4以上のモノオレフィンを酸化してジオレフィンを得るジオレフィン製造工程を有する、ジオレフィンの製造方法。
〔13〕
前項〔1〕~〔4〕のいずれか1項に記載の酸化物触媒を用いて、流動層反応器内で、プロピレン、イソブチレン、プロパノール、イソプロパノール、イソブタノール、及びt-ブチルアルコールからなる群より選ばれる1種以上と、分子状酸素と、アンモニアと、を反応させて不飽和ニトリルを得る不飽和ニトリル製造工程を有する、不飽和ニトリルの製造方法。 That is, the present invention is as follows.
[1]
An oxide catalyst used for producing an unsaturated aldehyde, diolefin, or unsaturated nitrile from an olefin and / or an alcohol, the oxide catalyst satisfying the following (1) to (3):
(1) Contains molybdenum, bismuth, iron, cobalt, and element A (except for potassium, cesium, and rubidium) having an ionic radius greater than 0.96 、.
(2) The atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ≦ a ≦ 5, the atomic ratio b of the iron is 1.5 ≦ b ≦ 6, and the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of cobalt is 1 ≦ d ≦ 8,
(3) It includes a disorder phase composed of a crystal system containing the molybdenum, the bismuth, the iron, and the element A.
[2]
The diffraction angles (2θ) in X-ray diffraction are 18.30 ° ± 0.2 °, 28.20 ° ± 0.2 °, 33.65 ° ± 0.2 °, and 46.15 ° ± 0.2. Has a single peak in the range of °, and
The intensity ratio (Ia / Ib) between the intensity (Ia) of peak a at 2θ = 33.65 ° ± 0.2 ° and the intensity (Ib) of peak b at 2θ = 34.10 ° ± 0.2 ° The oxide catalyst according to [1], which is 2.0 or more.
[3]
The oxide catalyst according to [1] or [2], which has a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b A c Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium), Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ≦ a ≦ 5, and Fe atomic ratio b is 1.5 ≦ b. ≦ 6, the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of Co is 1 ≦ d ≦ 8, the atomic ratio e of the element B is 0 ≦ e <3, The atomic ratio f of C is 0 ≦ f ≦ 2. , The ratio of Fe / Co is 0.8 ≦ b / d, g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.)
[4]
4. The oxide catalyst according to any one of items [1] to [3], further including at least one selected from the group consisting of silica, alumina, titania, and zirconia as a support.
[5]
A mixing step of mixing a raw material constituting a catalyst containing molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius larger than 0.96 た だ し (excluding potassium, cesium, and rubidium) to obtain a raw slurry ,
A drying step of drying the obtained raw material slurry to obtain a dried product,
A firing step of firing the obtained dried body;
Have
The said baking process is a manufacturing method of an oxide catalyst which has a temperature rising process which heats up the said dry body gradually over 100 hours from 100 degreeC to 200 degreeC.
[6]
The method for producing an oxide catalyst according to [5] above, wherein the pH of the raw slurry is 8 or less.
[7]
The calcining step includes calcining at a temperature of 200 to 300 ° C. to obtain a calcined product,
A main firing step of subjecting the obtained temporary fired body to a main firing at a temperature of 300 ° C. or higher to obtain a catalyst;
The method for producing an oxide catalyst according to [5] or [6] above.
[8]
Production of an unsaturated aldehyde comprising an unsaturated aldehyde production step of obtaining an unsaturated aldehyde by oxidizing an olefin and / or alcohol using the oxide catalyst according to any one of [1] to [4] above Method.
[9]
The method for producing an unsaturated aldehyde according to [8] above, wherein the olefin and / or the alcohol is at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol. .
[10]
In the unsaturated aldehyde production process, in the fluidized bed reactor, the olefin and / or the alcohol and the oxygen source are subjected to a gas phase catalytic oxidation reaction, and the product gas containing the unsaturated aldehyde from the fluidized bed reactor. The method for producing an unsaturated aldehyde as described in [8] or [9] above, wherein the method comprises an outflow step for allowing the effluent to flow.
[11]
The reaction temperature of the gas phase catalytic oxidation reaction is 400 to 500 ° C .;
The oxygen concentration in the product gas flowing out of the fluidized bed reactor is 0.03 to 0.5% by volume,
10. The method for producing an unsaturated aldehyde according to any one of [8] to [10] above.
[12]
A method for producing a diolefin, comprising the step of producing a diolefin by oxidizing a monoolefin having 4 or more carbon atoms using the oxide catalyst according to any one of [1] to [4] above .
[13]
From the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol in the fluidized bed reactor using the oxide catalyst according to any one of [1] to [4] above The manufacturing method of an unsaturated nitrile which has an unsaturated nitrile manufacturing process which makes 1 or more types chosen, molecular oxygen, and ammonia react, and obtains an unsaturated nitrile.
〔酸化物触媒〕
第1の実施形態に係る酸化物触媒について説明する。
第1の実施形態に係る酸化物触媒は、
オレフィン及び/又はアルコールから、不飽和アルデヒド又はジオレフィンを製造する際に用いられる酸化物触媒であって、下記(1)~(3)を満たす;
(1)モリブデン(以下、「Mo」ともいう。)、ビスマス(以下、「Bi」ともいう。)、鉄(以下、「Fe」ともいう。)、コバルト(以下、「Co」ともいう。)、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含有し、
(2)前記モリブデン12原子に対する、前記ビスマスの原子比aが1≦a≦5であり、前記鉄の原子比bが1.5≦b≦6であり、前記元素Aの原子比cが1≦c≦5であり、前記コバルトの原子比dが1≦d≦8であり、
(3)前記モリブデン、前記ビスマス、前記鉄、及び前記元素Aを含む結晶系からなるdisorder相を含む。 [First Embodiment]
[Oxide catalyst]
The oxide catalyst according to the first embodiment will be described.
The oxide catalyst according to the first embodiment is
An oxide catalyst used in producing an unsaturated aldehyde or diolefin from an olefin and / or an alcohol, which satisfies the following (1) to (3);
(1) Molybdenum (hereinafter also referred to as “Mo”), bismuth (hereinafter also referred to as “Bi”), iron (hereinafter also referred to as “Fe”), cobalt (hereinafter also referred to as “Co”). And an element A having an ionic radius larger than 0.96 Å (excluding potassium, cesium and rubidium),
(2) The atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ≦ a ≦ 5, the atomic ratio b of the iron is 1.5 ≦ b ≦ 6, and the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of cobalt is 1 ≦ d ≦ 8,
(3) It includes a disorder phase composed of a crystal system containing the molybdenum, the bismuth, the iron, and the element A.
不飽和アルデヒド、又はジオレフィンを製造する際に用いられる原料となるオレフィンとしては、特に限定されないが、例えば、プロピレン、n-ブテン、イソブチレン、n-ペンテン、n-ヘキセン、シクロヘキセンなどが挙げられる。このなかでも、プロピレン及びイソブチレンが好ましい。 (material)
The olefin that is a raw material used in producing an unsaturated aldehyde or diolefin is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, propylene and isobutylene are preferable.
第1の実施形態に係る酸化物触媒は、モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含有する。BiとMoとが共に活性種を形成するビスモリ系(Bi-Mo)触媒において、各金属元素が複合化するようにする観点から、Mo、Bi、Feの存在は不可欠である。 (I) Composition The oxide catalyst according to the first embodiment contains molybdenum, bismuth, iron, cobalt, and an element A (except for potassium, cesium, and rubidium) having an ionic radius larger than 0.96Å. . The presence of Mo, Bi, and Fe is indispensable from the viewpoint of making each metal element complex in a bismoly (Bi—Mo) catalyst in which Bi and Mo together form an active species.
第1の実施形態に係る酸化物触媒は、disorder相Bi3-xAxFe1Mo2O12を含む四成分複合酸化物を含有することが好ましい。disorder相Bi3-xAxFe1Mo2O12を含む四成分複合酸化物の生成の指標としては、X線回折(XRD)を用いることができる。disorder相Bi3Fe1Mo2O12を含む三成分複合酸化物の場合と同様に、第1の実施形態に係る酸化物触媒を結晶のX線回折の回折角2θ=10°~60°の範囲において測定すると、少なくとも18.30°±0.2°(101)面、28.20°±0.2°(112)面、33.65°±0.2°(200)面、46.15°±0.2°(204)面に単一ピークを有することが好ましい。特に、単一ピークは、各基準値±0.05°以内の位置に有することが好ましい。 (2) Crystal Structure The oxide catalyst according to the first embodiment preferably contains a quaternary composite oxide containing a disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 . X-ray diffraction (XRD) can be used as an index for producing a quaternary composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 . As in the case of the ternary composite oxide containing the disorder phase Bi 3 Fe 1 Mo 2 O 12 , the oxide catalyst according to the first embodiment is subjected to X-ray diffraction diffraction angle 2θ = 10 ° to 60 ° of the crystal. When measured in range, at least 18.30 ° ± 0.2 ° (101) plane, 28.20 ° ± 0.2 ° (112) plane, 33.65 ° ± 0.2 ° (200) plane, 46. It is preferable to have a single peak on the 15 ° ± 0.2 ° (204) plane. In particular, it is preferable to have a single peak at a position within each reference value ± 0.05 °.
本明細書中、「単一ピーク」とは、厳格に判断されるべきものではなく、その回折角において検出された主なピークが分裂していなければ、単一ピークと判断できる。すなわちピークが変曲点を有する場合であっても、単一ピークとみなすことができる。また、主なピークと比較して明らかに小さなピークが存在する場合、小さなピークは除外した上で、主なピークが単一か分裂かを判断することが望ましい。「小さなピーク」とは、所定の範囲の回折角において、主なピークの強度の50%未満の強度を有するピークをいう。 (Single peak)
In the present specification, the “single peak” should not be determined strictly, and can be determined as a single peak if the main peak detected at the diffraction angle is not split. That is, even if the peak has an inflection point, it can be regarded as a single peak. In addition, when there is a clearly small peak compared to the main peak, it is desirable to exclude the small peak and determine whether the main peak is single or split. “Small peak” refers to a peak having an intensity of less than 50% of the intensity of a main peak at a diffraction angle in a predetermined range.
下記組成式(1)
Mo12BiaFebAcCodBeCfOg (1)
(式中、Moはモリブデンであり、Biはビスマスであり、Feは鉄であり、元素Aはイオン半径が0.96Åよりも大きな元素(ただし、カリウム、セシウム及びルビジウムを除く)であり、Coはコバルトであり、元素Bはマグネシウム、亜鉛、銅、ニッケル、マンガン、クロム、及び錫からなる群より選ばれる少なくとも1種の元素であり、元素Cはカリウム、セシウム、及びルビジウムからなる群より選ばれる少なくとも1種の元素であり、a~gは、Mo12原子に対する各元素の原子比であり、Biの原子比aは1≦a≦5であり、Feの原子比bは1.5≦b≦6であり、元素Aの原子比cは1≦c≦5であり、Coの原子比dは1≦d≦8であり、元素Bの原子比eは0≦e<3であり、元素Cの原子比fは0≦f≦2であり、Fe/Coの比は0.8≦b/dであり、gは酸素以外の構成元素の原子価によって決まる酸素の原子数である。) The oxide catalyst according to the first embodiment preferably has a composition represented by the following composition formula (1). When the oxide catalyst has a composition represented by the following composition formula (1), generation of unsaturated carboxylic acid and carbon dioxide is suppressed, and the selectivity of unsaturated aldehyde and / or diolefin tends to be improved. .
The following composition formula (1)
Mo 12 Bi a Fe b A c Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium), Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ≦ a ≦ 5, and Fe atomic ratio b is 1.5 ≦ b. ≦ 6, the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of Co is 1 ≦ d ≦ 8, the atomic ratio e of the element B is 0 ≦ e <3, The atomic ratio f of C is 0 ≦ f ≦ 2. , The ratio of Fe / Co is 0.8 ≦ b / d, g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.)
第1の実施形態における酸化物触媒は、金属酸化物を担持するための担体を含有してもよい。担体を含む触媒は、金属酸化物の高分散化の点、及び担持された金属酸化物に高い耐摩耗性を与えるという点で好ましい。ここで、押し出し成型法により触媒を成型する場合には担体を含むことが好ましいが、固定層反応器でメタクロレインを製造する際に、打錠成型した触媒にする場合には担体を含まなくてもよい。 (3) Components other than metal oxide The oxide catalyst in the first embodiment may contain a carrier for supporting a metal oxide. A catalyst containing a support is preferable in terms of high dispersion of the metal oxide and high wear resistance of the supported metal oxide. Here, when the catalyst is molded by an extrusion molding method, it is preferable to include a carrier. However, when producing methacrolein in a fixed bed reactor, when a tablet-molded catalyst is used, the carrier is not included. Also good.
第1の実施形態の酸化物触媒を成型して用いる場合、成型は打錠成型や押し出し成型など公知の方法で行われる。成型する際の形状としては、タブレット、ペレット、球、CDS(Computer Designed Shape)、トリローブ、クワードローブ、リング、HGS(High Geometric Surface)、クローバー、ハニカムなどが挙げられる。このなかでも、強度の観点から、CDS、リングが好ましい。 (4) Molding of oxide catalyst When the oxide catalyst of the first embodiment is molded and used, the molding is performed by a known method such as tableting molding or extrusion molding. Examples of the shape at the time of molding include tablets, pellets, spheres, CDS (Computer Designed Shape), trilobes, wardrobes, rings, HGS (High Geometric Surface), clovers, and honeycombs. Among these, CDS and ring are preferable from the viewpoint of strength.
上述のように、本発明者らは、元素A、Bi、Fe及びMoを含む、disorder相Bi3-xAxFe1Mo2O12を得ることに着目し、その組成比や調製方法を総合的に検討した。 [2] Method for Producing Oxide Catalyst As described above, the inventors focus on obtaining a disorderer phase Bi 3-x A x Fe 1 Mo 2 O 12 containing elements A, Bi, Fe and Mo. The composition ratio and preparation method were comprehensively studied.
モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含む、触媒を構成する原料を混合して原料スラリーを得る混合工程と、
得られた該原料スラリーを乾燥して乾燥体を得る乾燥工程と、
得られた該乾燥体を焼成する焼成工程と、
を有し、
前記焼成工程において、前記乾燥体を100℃から200℃まで1時間以上掛けて徐々に昇温する昇温工程を有する。 The manufacturing method of the oxide catalyst in the first embodiment is as follows:
A mixing step of mixing a raw material constituting a catalyst containing molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius larger than 0.96 た だ し (excluding potassium, cesium, and rubidium) to obtain a raw slurry ,
A drying step of drying the obtained raw material slurry to obtain a dried product,
A firing step of firing the obtained dried body;
Have
The firing step includes a temperature raising step of gradually raising the temperature of the dried body from 100 ° C. to 200 ° C. over 1 hour or more.
混合工程は、モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含む、触媒を構成する各金属元素の触媒原料を混合して原料スラリーを得る工程である。モリブデン、ビスマス、鉄、コバルト、元素A、ルビジウム、セシウム、カリウム、マグネシウム、銅、ニッケル、クロム、マンガン、鉛、アルカリ土類金属、及び希土類元素の各元素源としては、水又は硝酸に可溶な、アンモニウム塩、硝酸塩、塩酸塩、有機酸塩、酸化物、水酸化物、炭酸塩が挙げられる。 (1) Mixing step The mixing step includes molybdenum, bismuth, iron, cobalt, and each metal element that constitutes the catalyst, including element A (excluding potassium, cesium, and rubidium) having an ionic radius greater than 0.96 Å. This is a step of mixing the catalyst raw materials to obtain a raw material slurry. Molybdenum, bismuth, iron, cobalt, element A, rubidium, cesium, potassium, magnesium, copper, nickel, chromium, manganese, lead, alkaline earth metals, and rare earth elements are soluble in water or nitric acid. Examples thereof include ammonium salts, nitrates, hydrochlorides, organic acid salts, oxides, hydroxides, and carbonates.
乾燥工程は、混合工程で得られた原料スラリーを乾燥して乾燥体を得る工程である。乾燥方法は、特に制限はなく一般に用いられている方法によって行うことができ、例えば、蒸発乾固法、噴霧乾燥法、減圧乾燥法など任意の方法が挙げられる。噴霧乾燥法としては、特に限定されないが、例えば、通常工業的に実施される遠心方式、二流体ノズル方式、及び高圧ノズル方式等の方法が挙げられる。この際の乾燥熱源としては、スチーム、電気ヒーター等によって加熱された空気を用いることが好ましい。この際、噴霧乾燥装置の乾燥機入口の温度は、通常150~400℃であり、好ましくは180~400℃であり、より好ましくは200~350℃である。 (2) Drying process A drying process is a process of drying the raw material slurry obtained at the mixing process, and obtaining a dry body. The drying method is not particularly limited and can be carried out by a commonly used method, and examples thereof include an arbitrary method such as evaporation to dryness, spray drying, and reduced pressure drying. Although it does not specifically limit as a spray-drying method, For example, methods, such as a centrifugal system, a two-fluid nozzle system, a high pressure nozzle system, etc. which are usually implemented industrially, are mentioned. As the drying heat source at this time, it is preferable to use air heated by steam, an electric heater or the like. At this time, the temperature at the inlet of the dryer of the spray dryer is usually 150 to 400 ° C., preferably 180 to 400 ° C., more preferably 200 to 350 ° C.
焼成工程は、乾燥工程で得られた乾燥体を焼成する工程である。焼成は、回転炉、トンネル炉、マッフル炉等の焼成炉を用いて行うことができる。焼成工程は、乾燥体を100から200℃まで1時間以上掛けて徐々に昇温する昇温工程を有する。この昇温工程を経ることでBi、Mo、Fe及び元素Aの4成分の元素が原子レベルで均一に混ざり合い、disorder相Bi3-xAxFe1Mo2O12の結晶構造が生成されやすくなる。本明細書中、「徐々に昇温」とは、昇温時間にして通常1h~10hかけて設定温度まで昇温することをいう。昇温レートは常に一定である必要はない。昇温時間は、通常1h~10hであり、好ましくは1h~5hであり、より好ましくは2h~4hである。 (3) Firing step The firing step is a step of firing the dried body obtained in the drying step. Firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace. The firing step has a temperature raising step of gradually raising the temperature of the dried body from 100 to 200 ° C. over 1 hour or more. Through this heating process, the four components of Bi, Mo, Fe and element A are uniformly mixed at the atomic level, and the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is generated. It becomes easy. In this specification, “gradual increase in temperature” means that the temperature is increased to a set temperature usually over 1 h to 10 h as a temperature increase time. The heating rate need not always be constant. The temperature raising time is usually 1h to 10h, preferably 1h to 5h, more preferably 2h to 4h.
第1の実施形態に係る酸化物触媒を用い、プロピレン及びイソブチレンからなる群より選ばれる少なくとも1種のオレフィン、及び/又はイソブタノール、t-ブチルアルコールを酸化反応させることにより、不飽和アルデヒドを製造することができる。以下、その具体例について説明するが、不飽和アルデヒドの製造方法は、以下の具体例に限定されるものではない。 [3] Method for Producing Unsaturated Aldehyde Oxidation reaction of at least one olefin selected from the group consisting of propylene and isobutylene and / or isobutanol and t-butyl alcohol using the oxide catalyst according to the first embodiment By making it, an unsaturated aldehyde can be manufactured. Hereinafter, although the specific example is demonstrated, the manufacturing method of unsaturated aldehyde is not limited to the following specific examples.
メタクロレインは、例えば、第1の実施形態に係る酸化物触媒を用いて、イソブチレン、イソブタノール、t-ブチルアルコールの気相接触酸化反応を行うことにより得ることができる。気相接触酸化反応は、酸化物触媒存在下で、1~10容量%のイソブチレン、イソブタノール、t-ブチルアルコール、又はこれらの混合ガスに対して、分子状酸素濃度が1~20容量%になるように、分子状酸素含有ガスと希釈ガスを添加した原料ガスを、固定層反応器内の触媒層に導入することで行うことができる。反応温度は250~480℃、反応圧力は常圧~5気圧の圧力、空間速度は400~4000/hr[Normal temperature pressure (NTP)条件下]とすることができる。酸素と、イソブチレン、イソブタノール、t-ブチルアルコール、又はこれらの混合ガスのモル比(酸素/イソブチレン、イソブタノール、t-ブチルアルコール、又はこれらの混合ガス)は、不飽和アルデヒドの収率を向上させるために反応器の出口酸素濃度を制御する観点から、通常1.0~2.0であり、好ましくは1.1~1.8であり、より好ましくは1.2~1.8である。 (1) Method for producing methacrolein Methacrolein can be obtained, for example, by performing a gas phase catalytic oxidation reaction of isobutylene, isobutanol, and t-butyl alcohol using the oxide catalyst according to the first embodiment. it can. In the gas phase catalytic oxidation reaction, the molecular oxygen concentration is 1 to 20% by volume with respect to 1 to 10% by volume of isobutylene, isobutanol, t-butyl alcohol, or a mixed gas thereof in the presence of an oxide catalyst. As described above, the raw material gas to which the molecular oxygen-containing gas and the dilution gas are added can be introduced into the catalyst layer in the fixed bed reactor. The reaction temperature can be 250 to 480 ° C., the reaction pressure can be normal pressure to 5 atmospheres, and the space velocity can be 400 to 4000 / hr (under normal temperature pressure (NTP) conditions). The molar ratio of oxygen to isobutylene, isobutanol, t-butyl alcohol, or mixed gas (oxygen / isobutylene, isobutanol, t-butyl alcohol, or mixed gas) improves the yield of unsaturated aldehydes. In view of controlling the oxygen concentration at the outlet of the reactor, it is usually 1.0 to 2.0, preferably 1.1 to 1.8, more preferably 1.2 to 1.8. .
プロピレンの気相接触酸化によりアクロレインを製造する際の条件等に特に制限はなく、プロピレンの気相接触酸化によりアクロレインを製造する際に一般に用いられている方法によって行うことができる。例えば、プロピレン1~15容量%、分子状酸素3~30容量%、水蒸気0~60容量%、並びに、窒素及び炭酸ガスなどの不活性ガス20~80容量%、などを含む混合ガスを、反応器の触媒層に250~450℃、0.1~1MPaの加圧下、空間速度(SV)300~5000hr-1で導入すればよい。また、反応器については、一般の固定層反応器、流動層反応器あるいは移動層反応器を用いることができる。 (2) Acrolein production method There are no particular restrictions on the conditions for producing acrolein by vapor phase catalytic oxidation of propylene, and the method is generally used when producing acrolein by vapor phase catalytic oxidation of propylene. Can do. For example, a mixed gas containing 1 to 15% by volume of propylene, 3 to 30% by volume of molecular oxygen, 0 to 60% by volume of water vapor, and 20 to 80% by volume of an inert gas such as nitrogen and carbon dioxide is reacted. The catalyst may be introduced at a space velocity (SV) of 300 to 5000 hr −1 under a pressure of 250 to 450 ° C. and a pressure of 0.1 to 1 MPa. Moreover, about a reactor, a general fixed bed reactor, a fluidized bed reactor, or a moving bed reactor can be used.
第1の実施形態に係るジオレフィンの製造方法は、第1の実施形態に係る酸化物触媒を用いて、炭素数4以上のモノオレフィンを酸化してジオレフィンを得るジオレフィン製造工程を有する。ジオレフィン製造工程は、より具体的には、第1の実施形態に係る酸化物触媒の存在下、炭素数4以上のモノオレフィンと、酸素源と、を気相接触酸化反応させることによりジオレフィンを得る工程である。 (3) Diolefin Production Method The diolefin production method according to the first embodiment is obtained by oxidizing a monoolefin having 4 or more carbon atoms using the oxide catalyst according to the first embodiment. Having a diolefin production process. More specifically, in the diolefin production process, a diolefin is produced by subjecting a monoolefin having 4 or more carbon atoms and an oxygen source to a gas phase catalytic oxidation reaction in the presence of the oxide catalyst according to the first embodiment. It is the process of obtaining.
第2の実施形態に係る酸化物触媒(以下、「アンモ酸化触媒」ともいう。)について説明する。
第2の実施形態に係る酸化物触媒は、
オレフィン及び/又はアルコールから、不飽和ニトリルを製造する際に用いられる酸化物触媒であって、下記(1)~(3)を満たす;
(1)モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(カリウム、セシウム及びルビジウムを除く)を含有し、
(2)前記モリブデン12原子に対する、前記ビスマスの原子比aが1≦a≦5であり、前記鉄の原子比bが1.5≦b≦6であり、前記元素Aの原子比cが1≦c≦5であり、前記コバルトの原子比dが1≦d≦8であり、
(3)前記モリブデン、前記ビスマス、前記鉄、及び前記元素Aを含む結晶系からなるdisorder相を含む。 [Second Embodiment]
The oxide catalyst according to the second embodiment (hereinafter also referred to as “ammoxidation catalyst”) will be described.
The oxide catalyst according to the second embodiment is
An oxide catalyst used in the production of an unsaturated nitrile from an olefin and / or an alcohol, which satisfies the following (1) to (3);
(1) containing molybdenum, bismuth, iron, cobalt, and an element A (excluding potassium, cesium and rubidium) having an ionic radius larger than 0.96 、,
(2) The atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ≦ a ≦ 5, the atomic ratio b of the iron is 1.5 ≦ b ≦ 6, and the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of cobalt is 1 ≦ d ≦ 8,
(3) It includes a disorder phase composed of a crystal system containing the molybdenum, the bismuth, the iron, and the element A.
不飽和ニトリルを製造する際に用いられる原料となるオレフィンとしては、特に限定されないが、例えば、プロピレン、n-ブテン、イソブチレン、n-ペンテン、n-ヘキセン、シクロヘキセンなどが挙げられる。このなかでも、プロピレン及びイソブチレンが好ましい。 (material)
The olefin that is a raw material used in producing the unsaturated nitrile is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, propylene and isobutylene are preferable.
第1の実施形態に係る酸化物触媒は、モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(カリウム、セシウム及びルビジウムを除く)を含有する。BiとMoとが共に活性種を形成するビスモリ系(Bi-Mo)触媒において、各金属元素が複合化するようにする観点から、Mo、Bi、Feの存在は不可欠である。 (1) Composition The oxide catalyst according to the first embodiment contains molybdenum, bismuth, iron, cobalt, and an element A (excluding potassium, cesium, and rubidium) having an ionic radius greater than 0.96%. The presence of Mo, Bi, and Fe is indispensable from the viewpoint of making each metal element complex in a bismoly (Bi—Mo) catalyst in which Bi and Mo together form an active species.
なお、イオン半径は、例えば、「セラミックスの化学」、柳田博明編、第14~17頁、丸善株式会社等に記載されている。 The atomic ratio c of the element A to 12 atoms of molybdenum is 1 ≦ c ≦ 5, preferably 1 ≦ d ≦ 4, and more preferably 1.5 ≦ d ≦ 3. When the atomic ratio c is in the above range, a quaternary composite oxide containing a composite disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is easily formed. Taking the case where La is used as the element A as an example, a quaternary complex oxide containing the disorder phase Bi 3-x La x Fe 1 Mo 2 O 12 is formed. By appropriately laminating La to a ternary complex oxide containing the disorder phase Bi 3 Fe 1 Mo 2 O 12 , Bi 3+ (ionic radius is 0.96Å) is replaced with La 3+ having a larger ionic radius, An ammoxidation catalyst having not only high activity and selectivity but also reduction resistance can be obtained. When La 3+ is not included, the order phase Bi 3 Fe 1 Mo 2 O 12 is decomposed into FeMoO 4 , MoO 2 , Bi 2 O 3 and metal Bi by reduction with a reaction gas in an industrial long-term operation. However, if La having an ion radius slightly larger than Bi coexists, redox occurs between Fe and La, so that decomposition due to reduction of the reaction gas is suppressed, and the disorder phase Bi 3-x La x Fe 1 Mo is suppressed. Since the structure of 2 O 12 is maintained, it is not decomposed into FeMoO 4 , MoO 2 , Bi 2 O 3 or metal Bi.
The ion radius is described, for example, in “Ceramics Chemistry”, Hiroaki Yanagida, pages 14-17, Maruzen Co., Ltd. and the like.
第2の実施形態に係るアンモ酸化触媒は、disorder相Bi3-xAxFe1Mo2O12を含む四成分複合酸化物を含有することが好ましい。disorder相Bi3-xAxFe1Mo2O12を含む四成分複合酸化物の生成の指標としては、X線回折(XRD)を用いることができる。disorder相Bi3Fe1Mo2O12を含む三成分複合酸化物の場合と同様に、第2の実施形態に係るアンモ酸化触媒の結晶をX線回折の回折角2θ=10°~60°の範囲を測定すると、disorder相Bi3-xAxFe1Mo2O12を含む四成分複合酸化物が生成している場合には、少なくとも18.30°±0.2°(101)面、28.20°±0.2°(112)面、33.65°±0.2°(200)面、46.15°±0.2°(204)面に単一ピークが確認できる。特に、単一ピークは、各基準値±0.05°以内の位置に有することが好ましい。 (2) Crystal Structure The ammoxidation catalyst according to the second embodiment preferably contains a quaternary composite oxide containing a disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 . X-ray diffraction (XRD) can be used as an index for producing a quaternary composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 . Similarly to the case of the ternary composite oxide containing the disorder phase Bi 3 Fe 1 Mo 2 O 12 , the crystal of the ammoxidation catalyst according to the second embodiment has an X-ray diffraction angle of 2θ = 10 ° to 60 °. When the range is measured, when a quaternary composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 is formed, at least 18.30 ° ± 0.2 ° (101) plane, Single peaks can be confirmed on the 28.20 ° ± 0.2 ° (112) plane, the 33.65 ° ± 0.2 ° (200) plane, and the 46.15 ° ± 0.2 ° (204) plane. In particular, it is preferable to have a single peak at a position within each reference value ± 0.05 °.
Mo12BiaFebAcCodBeCfOg (2)
(式中、Moはモリブデンであり、Biはビスマスであり、Feは鉄であり、元素Aはイオン半径が0.96Åよりも大きな元素(ただし、カリウム、セシウム及びルビジウムを除く)であり、Coはコバルトであり、元素Bはマグネシウム、亜鉛、銅、ニッケル、マンガン、クロム、及び錫からなる群より選ばれる少なくとも1種の元素であり、元素Cはカリウム、セシウム、及びルビジウムからなる群より選ばれる少なくとも1種の元素であり、a~gは、Mo12原子に対する各元素の原子比であり、Biの原子比aは1≦a≦5であり、Feの原子比bは1.5≦b≦6であり、元素Aの原子比cは1≦c≦5であり、Coの原子比dは1≦d≦8であり、元素Bの原子比eは0≦e<3であり、元素Cの原子比fは0≦f≦2であり、Fe/Coの比は0.8≦b/dであり、gは酸素以外の構成元素の原子価によって決まる酸素の原子数である。) The ammoxidation catalyst according to the second embodiment preferably includes a metal oxide having a composition represented by the following composition formula (2). When the ammoxidation catalyst contains a metal oxide having a composition represented by the following composition formula (2), the selectivity of unsaturated nitrile tends to be improved.
Mo 12 Bi a Fe b A c Co d B e C f O g (2)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium), Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ≦ a ≦ 5, and Fe atomic ratio b is 1.5 ≦ b. ≦ 6, the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of Co is 1 ≦ d ≦ 8, the atomic ratio e of the element B is 0 ≦ e <3, The atomic ratio f of C is 0 ≦ f ≦ 2. , The ratio of Fe / Co is 0.8 ≦ b / d, g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.)
第2の実施形態におけるアンモ酸化触媒は、金属酸化物を担持するための担体を含有してもよい。担体を含む触媒は、金属酸化物の高分散化の点、及び担持された金属酸化物に高い耐摩耗性を与えるという点で好ましい。 (3) Components other than metal oxide The ammoxidation catalyst in the second embodiment may contain a carrier for supporting the metal oxide. A catalyst containing a support is preferable in terms of high dispersion of the metal oxide and high wear resistance of the supported metal oxide.
第2の本実施態様実施形態におけるアンモ酸化触媒の製造方法は、
モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含む、触媒を構成する原料を混合して原料スラリーを得る混合工程と、
得られた該原料スラリーを乾燥して乾燥体を得る乾燥工程と、
得られた該乾燥体を焼成する焼成工程と、
を有し、
前記焼成工程において、前記乾燥体を100℃から200℃まで1時間以上掛けて徐々に昇温する昇温工程を有する。第2の実施形態に係るアンモ酸化触媒の製造方法の詳細については、第1の実施形態と同様である。 [2] Method for Producing Ammoxidation Catalyst A method for producing an ammoxidation catalyst in the second embodiment of the present invention is as follows.
A mixing step of mixing a raw material constituting a catalyst containing molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius larger than 0.96 た だ し (excluding potassium, cesium, and rubidium) to obtain a raw slurry ,
A drying step of drying the obtained raw material slurry to obtain a dried product,
A firing step of firing the obtained dried body;
Have
The firing step includes a temperature raising step of gradually raising the temperature of the dried body from 100 ° C. to 200 ° C. over 1 hour or more. The details of the method for producing an ammoxidation catalyst according to the second embodiment are the same as those of the first embodiment.
第2の実施形態に係る不飽和ニトリルの製造方法は、第2の実施形態に係る酸化物触媒を用いて、流動層反応器内で、オレフィン及び/又はアルコールと、分子状酸素と、アンモニアと、を反応させて不飽和ニトリルを得る不飽和ニトリル製造工程を有する。 [3] Method for Producing Unsaturated Nitrile The method for producing an unsaturated nitrile according to the second embodiment uses an oxide catalyst according to the second embodiment and olefin and / or alcohol in a fluidized bed reactor. And an unsaturated nitrile production step of obtaining unsaturated nitrile by reacting molecular oxygen with ammonia.
〔不飽和アルデヒドの製造方法〕
第3の実施形態に係る不飽和アルデヒドの製造方法は、
第1の実施形態に係る酸化物触媒を用いて、オレフィン及び/又はアルコールを酸化して不飽和アルデヒドを得る不飽和アルデヒド製造工程を有する。 [Third Embodiment]
[Method for producing unsaturated aldehyde]
The method for producing an unsaturated aldehyde according to the third embodiment,
Using the oxide catalyst which concerns on 1st Embodiment, it has an unsaturated aldehyde manufacturing process which oxidizes an olefin and / or alcohol and obtains an unsaturated aldehyde.
前記流動層反応器から流出する前記生成ガス中の酸素濃度が0.03~0.5体積%である、ことが好ましい。
以下、より詳細に説明する。 Furthermore, the reaction temperature of the gas phase catalytic oxidation reaction is 400 to 500 ° C.
It is preferable that the oxygen concentration in the product gas flowing out from the fluidized bed reactor is 0.03 to 0.5% by volume.
This will be described in more detail below.
原料のオレフィンとしては、特に限定されないが、例えば、プロピレン、n-ブテン、イソブチレン、n-ペンテン、n-ヘキセン、シクロヘキセンなどが挙げられる。このなかでも、プロピレン及びイソブチレンからなる群より選ばれる1種以上の化合物であることが好ましい。このようなオレフィンを用いることにより、不飽和アルデヒドの収率がより向上する傾向にある。 [Olefin]
The raw material olefin is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Of these, one or more compounds selected from the group consisting of propylene and isobutylene are preferable. By using such an olefin, the yield of unsaturated aldehyde tends to be further improved.
原料のアルコールとしては、特に限定されないが、例えば、プロパノール、ブタノール、イソブタノール、t-ブチルアルコールなどが挙げられる。このなかでも、プロパノール、イソブタノール及びt-ブチルアルコールからなる群より選ばれる1種以上の化合物が好ましい。このようなアルコールを用いることにより、不飽和アルデヒドの収率がより向上する傾向にある。 〔alcohol〕
The raw material alcohol is not particularly limited, and examples thereof include propanol, butanol, isobutanol, t-butyl alcohol, and the like. Of these, one or more compounds selected from the group consisting of propanol, isobutanol and t-butyl alcohol are preferred. By using such alcohol, the yield of unsaturated aldehyde tends to be further improved.
第3の実施形態に係る不飽和アルデヒドの製造方法においては、オレフィン及び/又はアルコールと酸素源とを、酸化物触媒を用いて気相接触酸化反応させ、不飽和アルデヒドを製造する。この気相接触反応における酸素源としては、特に限定されないが、例えば、分子状酸素含有ガスと希釈ガスとの混合ガスを使用することができる。 [Oxygen source]
In the method for producing an unsaturated aldehyde according to the third embodiment, an olefin and / or alcohol and an oxygen source are subjected to a gas phase catalytic oxidation reaction using an oxide catalyst to produce an unsaturated aldehyde. Although it does not specifically limit as an oxygen source in this gaseous-phase contact reaction, For example, the mixed gas of molecular oxygen containing gas and dilution gas can be used.
0.01<分子状酸素含有ガス/(分子状酸素含有ガス+希釈ガス)<0.3 Regarding the mixing ratio of the molecular oxygen-containing gas and the dilution gas in the mixed gas, it is preferable that the following inequality condition is satisfied by the volume ratio.
0.01 <molecular oxygen-containing gas / (molecular oxygen-containing gas + dilution gas) <0.3
第3の実施形態に係る不飽和アルデヒドの製造方法は、流動層反応器(以下、単に「反応器」ともいう。)を用いることが好ましい。流動層反応器とは、反応器内にガス分散器、内挿物、サイクロンを主要構成要素として有し、酸化物触媒を流動させつつ、原料であるガスと接触させる構造を有する装置である。より具体的には、流動層ハンドブック(株式会社培風館刊、1999年)等に記載の流動層反応器等が使用可能である。このなかでも、特に気泡流動層方式の流動層反応器が適している。発生する反応熱の除熱は流動層反応器に内挿した冷却管を用いて行うことができる。 [Fluidized bed reactor]
The method for producing an unsaturated aldehyde according to the third embodiment preferably uses a fluidized bed reactor (hereinafter also simply referred to as “reactor”). The fluidized bed reactor is an apparatus having a structure in which a gas disperser, an interpolator, and a cyclone are included as main components in the reactor, and an oxide catalyst is made to flow while contacting with a raw material gas. More specifically, a fluidized bed reactor described in a fluidized bed handbook (published by Baifukan Co., Ltd., 1999) or the like can be used. Among these, a fluidized bed reactor of a bubble fluidized bed type is particularly suitable. The generated heat of reaction can be removed by using a cooling pipe inserted in the fluidized bed reactor.
第3の実施形態に係る不飽和アルデヒドの製造方法においては、気相接触反応の反応温度は、好ましくは400~500℃であり、より好ましくは420~470℃であり、さらに好ましくは430~450℃である。反応温度が400℃以上であることにより、転化率及び反応速度がより向上し、不飽和アルデヒドの収率がさらに向上する傾向にある。反応温度が500℃以下であることにより、生成した不飽和アルデヒドの燃焼分解がより抑制される傾向にある。気相接触酸化反応の反応温度は、流動層反応器に内挿した温度計により測定することができる。 [Reaction temperature of gas phase catalytic oxidation reaction]
In the method for producing an unsaturated aldehyde according to the third embodiment, the reaction temperature of the gas phase catalytic reaction is preferably 400 to 500 ° C., more preferably 420 to 470 ° C., and further preferably 430 to 450. ° C. When the reaction temperature is 400 ° C. or higher, the conversion rate and reaction rate are further improved, and the yield of unsaturated aldehyde tends to be further improved. When the reaction temperature is 500 ° C. or lower, combustion decomposition of the generated unsaturated aldehyde tends to be further suppressed. The reaction temperature of the gas phase catalytic oxidation reaction can be measured with a thermometer inserted in the fluidized bed reactor.
オレフィン及び/又はアルコール、並びに酸素源の導入方法は、特に限定されず、たとえば、酸化物触媒を充填した流動層反応器へ、オレフィン及び/又はアルコールを含むガスと、空気又は酸素濃度を高めたガスとを予め混合して導入してもよいし、それぞれのガスを独立に導入してもよい。反応に供するガスは反応器に導入した後に所定の反応温度に昇温することも、予熱して反応器に導入することもできる。このなかでも、連続して効率的に反応させるために、予熱して反応器に導入することが好ましい。 [Olefin and / or alcohol and oxygen source introduction method]
The method of introducing the olefin and / or alcohol and the oxygen source is not particularly limited. For example, the gas containing the olefin and / or alcohol and the air or oxygen concentration are increased to the fluidized bed reactor filled with the oxide catalyst. Gases may be mixed and introduced in advance, or each gas may be introduced independently. The gas used for the reaction can be heated to a predetermined reaction temperature after being introduced into the reactor, or can be preheated and introduced into the reactor. Among these, in order to continuously and efficiently react, it is preferable to preheat and introduce into the reactor.
流動層反応器から流出する生成ガス中の酸素濃度は、好ましくは0.03~0.5体積%であり、より好ましくは0.03~0.2体積%であり、さらに好ましくは0.05~0.1体積%である。反応器出口酸素濃度が0.5体積%以下であることにより、触媒が過剰に還元されることをより抑制できる傾向にある。また、0.03体積%以上であることにより、触媒が過剰に酸化されることが抑制され、いずれの場合も、不飽和アルデヒドの収率がより向上する傾向にある。反応器出口酸素濃度を上記範囲に調整することにより、酸化還元度のバランスを崩すことなく、不飽和アルデヒドの燃焼分解を抑制することができる。 [Oxygen concentration in product gas flowing out from fluidized bed reactor]
The oxygen concentration in the product gas flowing out from the fluidized bed reactor is preferably 0.03 to 0.5% by volume, more preferably 0.03 to 0.2% by volume, and even more preferably 0.05. ~ 0.1% by volume. When the reactor outlet oxygen concentration is 0.5% by volume or less, excessive reduction of the catalyst tends to be further suppressed. Moreover, it is suppressed that a catalyst is oxidized excessively by being 0.03 volume% or more, and it exists in the tendency which the yield of unsaturated aldehyde improves more in any case. By adjusting the reactor outlet oxygen concentration within the above range, the combustion decomposition of unsaturated aldehyde can be suppressed without losing the balance of the redox degree.
接触時間(g・sec/cm2)=W/F*60*273.15/(273.15+T)*(P*1000+101.325)/101.325
(式中、Wは流動層反応器中の触媒充填量(g)、Fは原料混合ガス流量(cm2/min、NTP換算)、Tは反応温度(℃)、Pは反応圧力(MPa)を表す。) Conditions for adjusting the oxygen concentration at the outlet of the reactor include the amount of catalyst, contact time, reaction pressure, space velocity and the like as well as the conversion rate. By adjusting these conditions in combination, the oxygen concentration at the outlet of the reactor can be adjusted to an arbitrary value. For example, when the reaction is performed by adjusting the reaction temperature to 430 ° C. to 500 ° C. and the olefin and / or alcohol concentration to the range of 6 to 10% by volume, the following formula is used to adjust the reactor outlet oxygen concentration to the above range. the contact time is defined is preferably 5.0 (g · sec / cm 2 ) or less, 4.0 (g · sec / cm 2) , more preferably less, 3.0 (g · sec / cm 2) or less Further preferred.
Contact time (g · sec / cm 2 ) = W / F * 60 * 273.15 / (273.15 + T) * (P * 1000 + 101.325) /101.325
(Wherein, W is the catalyst filling amount (g) in the fluidized bed reactor, F is the raw material mixed gas flow rate (cm 2 / min, NTP conversion), T is the reaction temperature (° C.), and P is the reaction pressure (MPa). Represents.)
第3の実施形態で用いられる酸化物触媒としては、第1の実施形態に係る酸化物触媒を用いる。このなかでも、モリブデン、ビスマス、鉄、コバルト、及びランタノイド元素を含み、コバルトに対する鉄の原子比Fe/CoがFe/Co≧1を満たし、担体をさらに含む酸化物触媒を用いることが好ましい。 [Oxide catalyst]
As the oxide catalyst used in the third embodiment, the oxide catalyst according to the first embodiment is used. Among these, it is preferable to use an oxide catalyst that contains molybdenum, bismuth, iron, cobalt, and a lanthanoid element, the atomic ratio Fe / Co of iron to cobalt satisfies Fe / Co ≧ 1, and further includes a support.
Mo12BiaFebCodAcBeCfOg (1)
(式中、Moはモリブデン、Biはビスマス、Feは鉄、Coはコバルトであり、
Aは、ランタン、セリウム、プラセオジム、及びネオジムからなる群より選ばれる少なくとも1種のランタノイド元素を示し、
Bは、マグネシウム、亜鉛、銅、ニッケル、マンガン、カルシウム、ストロンチウム、バリウム、錫、及び鉛からなる群より選ばれる少なくとも1種の元素を示し、
Cは、カリウム、セシウム、及びルビジウムからなる群より選ばれる少なくとも1種の元素を示し、
a~gは、モリブデン12原子に対する各元素の原子比を示し、1≦a≦5、1.5≦b≦6、1≦d≦6、Fe/Co≧1、1≦c≦5、0≦e<3、及び0.01≦f≦2を満たし、
gは酸素以外の構成元素の原子価によって決まる酸素の原子数である。) The oxide catalyst used in the third embodiment preferably has a composition represented by the following formula (1).
Mo 12 Bi a Fe b Co d A c B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt,
A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium;
B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, calcium, strontium, barium, tin, and lead;
C represents at least one element selected from the group consisting of potassium, cesium, and rubidium;
a to g represent atomic ratios of each element to 12 atoms of molybdenum, 1 ≦ a ≦ 5, 1.5 ≦ b ≦ 6, 1 ≦ d ≦ 6, Fe / Co ≧ 1, 1 ≦ c ≦ 5, 0 ≦ e <3 and 0.01 ≦ f ≦ 2 are satisfied,
g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. )
第3の実施形態で用いる酸化物触媒は、担体に担持されたものである。担体は、担体と酸化物触媒の合計質量に対して20~80質量%が好ましく、30~70質量%がより好ましく、40~60質量%がさらに好ましい。担体の含有量が上記範囲内であることにより、不飽和アルデヒドの収率がより向上する傾向にある。Mo、Bi、Fe、Co、及びランタノイド原子を含有する酸化物を含む担持触媒は、公知の方法、例えば原料スラリーを調製する混合工程、該原料スラリーを噴霧乾燥する乾燥工程、及び乾燥工程で得られた乾燥品を焼成する焼成工程を包含する方法によって得ることができる。 (Carrier)
The oxide catalyst used in the third embodiment is supported on a carrier. The support is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass with respect to the total mass of the support and the oxide catalyst. When the content of the carrier is within the above range, the yield of the unsaturated aldehyde tends to be further improved. A supported catalyst containing an oxide containing Mo, Bi, Fe, Co, and a lanthanoid atom is obtained by a known method, for example, a mixing step for preparing a raw slurry, a drying step for spray-drying the raw slurry, and a drying step. The obtained dried product can be obtained by a method including a firing step.
第3の実施形態で用いる酸化物触媒は、特に限定されず、公知の方法により製造することができる。第3の実施形態で用いる酸化物触媒は、例えば、原料スラリーを調製する混合工程、該原料スラリーを噴霧乾燥して乾燥体を得る乾燥工程、及び該乾燥体を焼成する焼成工程を有する製造方法によって得ることができる。以下、上記工程を有する酸化物触媒の製造方法の好ましい態様について説明する。 [Production method of oxide catalyst]
The oxide catalyst used in the third embodiment is not particularly limited, and can be produced by a known method. The oxide catalyst used in the third embodiment includes, for example, a mixing step of preparing a raw material slurry, a drying step of spray-drying the raw material slurry to obtain a dry body, and a baking step of firing the dry body. Can be obtained by: Hereinafter, the preferable aspect of the manufacturing method of the oxide catalyst which has the said process is demonstrated.
以下に実施例Aを示して、第1の実施形態をより詳細に説明するが、第1の実施形態は以下に記載の実施例Aによって限定されるものではない。なお、酸化物触媒における酸素原子の原子比は、他の元素の原子価条件により決定されるものであり、実施例及び比較例においては、触媒の組成を表す式中、酸素原子の原子比は省略する。また、酸化物触媒における各元素の組成比は、仕込みの組成比から算出した。 [Example A]
Example A will be described below to describe the first embodiment in more detail. However, the first embodiment is not limited to Example A described below. The atomic ratio of oxygen atoms in the oxide catalyst is determined by the valence conditions of other elements, and in the examples and comparative examples, the atomic ratio of oxygen atoms in the formulas representing the catalyst composition Omitted. Further, the composition ratio of each element in the oxide catalyst was calculated from the composition ratio of preparation.
平均粒子径は、以下の式に従って計算により求めた。
平均粒子径[nm]=6000/(表面積[m2/g]×真密度(8.99g/cm3) <Measurement of average particle diameter>
The average particle size was obtained by calculation according to the following formula.
Average particle diameter [nm] = 6000 / (surface area [m 2 / g] × true density (8.99 g / cm 3 )
AS ONE製のpH METER KR5Eを用いて測定した。 <Measurement of pH>
It measured using pH METER KR5E made from AS ONE.
XRDの測定は、National Institute of Standards & Technologyが標準参照物質660として定めるところのLaB6化合物の(111)面、(200)面を測定し、それぞれの値を37.441°、43.506°となるように規準化した。 <Measurement of X-ray diffraction angle>
XRD was measured by measuring the (111) plane and the (200) plane of the LaB 6 compound as defined by National Institute of Standards & Technology as the standard reference material 660. The respective values were 37.441 °, 43.506 ° It was standardized to become.
実施例A及び比較例Aにおいて、反応成績を表すために用いた転化率、選択率、収率は次式で定義される。
転化率=(反応した原料のモル数/供給した原料のモル数)×100
選択率=(生成した化合物のモル数/反応した原料のモル数)×100
収率=(生成した化合物のモル数/供給した原料のモル数)×100 <Conversion rate, selectivity, yield>
In Example A and Comparative Example A, the conversion rate, selectivity, and yield used to express the reaction results are defined by the following formulas.
Conversion rate = (number of moles of reacted raw material / number of moles of supplied raw material) × 100
Selectivity = (number of moles of compound produced / number of moles of reacted raw material) × 100
Yield = (Mole number of produced compound / Mole number of supplied raw material) × 100
還元性評価は、触媒の耐還元性を加速的に評価するために実施した。酸素を含まないガス雰囲気の還元処理で触媒が還元され、反応評価条件に戻すことで触媒が再酸化される。これを繰り返すことで加速的な触媒の耐還元性を評価することができる。 <Reducibility evaluation>
The reduction evaluation was performed in order to accelerate the reduction resistance of the catalyst. The catalyst is reduced by the reduction treatment in the gas atmosphere not containing oxygen, and the catalyst is reoxidized by returning to the reaction evaluation condition. By repeating this, the reduction resistance of the accelerated catalyst can be evaluated.
La 1.14Å
Ce 1.07Å
Ca 1.03Å
Pb 1.24 Å
V 0.56 Å Moreover, the ionic radius of the element A used in Example A and Comparative Example A is as follows.
La 1.14Å
Ce 1.07mm
Ca 1.03Å
Pb 1.24 Å
V 0.56 Å
イオン交換水90.5gと、濃度30質量%の過酸化水素水127.5gとの混合液に、三酸化モリブデン54.5gを入れ、約70℃で攪拌混合し、溶解させて溶液(A液)を得た。また、10質量%の平均粒子径51nmの酸化ビスマス水分散液204.75g、15質量%の平均粒子径22nmの酸化コバルト水分散液54.3g、15質量%の平均粒子径39nmの酸化鉄水分散液57.1g、及び10質量%の平均粒子径40nmの酸化ランタン水分散液71.9g、及び10質量%の水酸化セシウム液4.3gを混合して溶液(B液)を得た。 [Example A1]
In a mixed solution of 90.5 g of ion-exchanged water and 127.5 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.5 g of molybdenum trioxide is stirred and mixed at about 70 ° C., dissolved, and dissolved (solution A). ) In addition, 204.75 g of 10% by mass bismuth oxide aqueous dispersion with an average particle size of 51 nm, 54.3 g of 15% by mass cobalt oxide aqueous dispersion with an average particle size of 22 nm, and 15% by mass of iron oxide water with an average particle size of 39 nm. 57.1 g of the dispersion, 71.9 g of a 10% by mass lanthanum oxide aqueous dispersion having an average particle size of 40 nm, and 4.3 g of a 10% by mass cesium hydroxide solution were mixed to obtain a solution (B solution).
約90℃の温水202.6gにヘプタモリブデン酸アンモニウム67.5gを溶解させた(A液)。また、硝酸ビスマス37.0g、硝酸セリウム22.0g、硝酸鉄51.3g、硝酸セシウム0.55g、及び硝酸コバルト37.2gを18質量%の硝酸水溶液41.9gに溶解させ、約90℃の温水206.2gを添加した(B液)。 [Example A2]
67.5 g of ammonium heptamolybdate was dissolved in 202.6 g of warm water at about 90 ° C. (solution A). Also, 37.0 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.3 g of iron nitrate, 0.55 g of cesium nitrate, and 37.2 g of cobalt nitrate were dissolved in 41.9 g of 18% by mass nitric acid aqueous solution, 206.2 g of warm water was added (Liquid B).
約90℃の温水199.2gにヘプタモリブデン酸アンモニウム66.4gを溶解させた(A液)。また、硝酸ビスマス47.0g、硝酸セリウム13.5g、硝酸カルシウム7.4g、硝酸鉄42.8g、硝酸ルビジウム1.56g、及び硝酸コバルト32.0gを18質量%の硝酸水溶液41.5gに溶解させ、約90℃の温水209.0gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.0に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで3hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、530℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Example A3]
66.4 g of ammonium heptamolybdate was dissolved in 199.2 g of warm water at about 90 ° C. (solution A). Also, 47.0 g of bismuth nitrate, 13.5 g of cerium nitrate, 7.4 g of calcium nitrate, 42.8 g of iron nitrate, 1.56 g of rubidium nitrate, and 32.0 g of cobalt nitrate were dissolved in 41.5 g of 18% by mass nitric acid aqueous solution. 209.0 g of warm water at about 90 ° C. was added (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 530 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
イオン交換水90.6gと、濃度30質量%の過酸化水素水127.6gとの混合液に、三酸化モリブデン54.5gを入れ、約70℃で攪拌混合し、溶解させて溶液(A液)を得た。また、10質量%の平均粒子径51nmの酸化ビスマス水分散液155.48g、硝酸鉛4.2g、15質量%の平均粒子径22nmの酸化コバルト水分散液62.4g、15質量%の平均粒子径39nmの酸化鉄水分散液50.4g、及び10質量%の平均粒子径40nmの酸化ランタン水分散液92.6g、及び10質量%の水酸化セシウム液4.3gを混合して溶液(B液)を得た。 [Example A4]
In a mixed solution of 90.6 g of ion-exchanged water and 127.6 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.5 g of molybdenum trioxide is added, stirred and mixed at about 70 ° C., dissolved, and dissolved (solution A). ) Also, 155.48 g of bismuth oxide aqueous dispersion with an average particle diameter of 51 nm of 10% by mass, 4.2 g of lead nitrate, 62.4 g of cobalt oxide aqueous dispersion with an average particle diameter of 22% by mass of 22 nm, and 15% by mass of average particles A solution (B) was prepared by mixing 50.4 g of an iron oxide aqueous dispersion with a diameter of 39 nm, 92.6 g of a 10% by mass lanthanum oxide aqueous dispersion with an average particle diameter of 40 nm, and 4.3 g of a 10% by mass cesium hydroxide liquid. Liquid).
約90℃の温水207.2gにヘプタモリブデン酸アンモニウム69.1gを溶解させた(A液)。また、硝酸ビスマス45.7g、硝酸セリウム14.0g、硝酸マンガン2.3g、硝酸鉄48.5g、硝酸セシウム0.57g、及び硝酸コバルト27.6gを18質量%の硝酸水溶液40.9gに溶解させ、約90℃の温水195.4gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.0に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで5hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、540℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Example A5]
69.1 g of ammonium heptamolybdate was dissolved in 207.2 g of warm water at about 90 ° C. (solution A). Also, 45.7 g of bismuth nitrate, 14.0 g of cerium nitrate, 2.3 g of manganese nitrate, 48.5 g of iron nitrate, 0.57 g of cesium nitrate, and 27.6 g of cobalt nitrate were dissolved in 40.9 g of 18% by mass nitric acid aqueous solution. Then, 195.4 g of warm water of about 90 ° C. was added (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 5 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
約90℃の温水211.2gにヘプタモリブデン酸アンモニウム70.4gを溶解させた(A液)。また、硝酸ビスマス34.0g、硝酸セリウム21.6g、硝酸鉄35.0g、硝酸セシウム0.58g、及び硝酸コバルト44.8gを18質量%の硝酸水溶液35.3gに溶解させ、約90℃の温水140.8gを添加した(B液)。 [Example A6]
70.4 g of ammonium heptamolybdate was dissolved in 21.2 g of warm water at about 90 ° C. (solution A). Also, 34.0 g of bismuth nitrate, 21.6 g of cerium nitrate, 35.0 g of iron nitrate, 0.58 g of cesium nitrate, and 44.8 g of cobalt nitrate were dissolved in 35.3 g of 18% by mass nitric acid aqueous solution. 140.8 g of warm water was added (Liquid B).
約90℃の温水193.1gにヘプタモリブデン酸アンモニウム64.4gを溶解させた(A液)。また、硝酸ビスマス37.0g、硝酸セリウム23.7g、硝酸鉄36.9g、硝酸セシウム0.41g、及び硝酸コバルト54.3gを18質量%の硝酸水溶液34.1gに溶解させ、約90℃の温水128.7gを添加した(B液)。 [Example A7]
64.4 g of ammonium heptamolybdate was dissolved in 193.1 g of warm water at about 90 ° C. (solution A). Also, 37.0 g of bismuth nitrate, 23.7 g of cerium nitrate, 36.9 g of iron nitrate, 0.41 g of cesium nitrate, and 54.3 g of cobalt nitrate were dissolved in 34.1 g of 18% by mass nitric acid aqueous solution. 128.7 g of warm water was added (Liquid B).
約90℃の温水208.8gにヘプタモリブデン酸アンモニウム69.6gを溶解させた(A液)。また、硝酸ビスマス28.6g、硝酸セリウム28.3g、硝酸マグネシウム10.9g、硝酸鉄38.3g、硝酸ルビジウム1.43g、及び硝酸ニッケル38.5gを18質量%の硝酸水溶液41.9gに溶解させ、約90℃の温水200.3gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.2に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで5hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、530℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A1]
69.6 g of ammonium heptamolybdate was dissolved in 208.8 g of warm water at about 90 ° C. (solution A). Also, 28.6 g of bismuth nitrate, 28.3 g of cerium nitrate, 10.9 g of magnesium nitrate, 38.3 g of iron nitrate, 1.43 g of rubidium nitrate, and 38.5 g of nickel nitrate were dissolved in 41.9 g of 18% by mass nitric acid aqueous solution. 200.3 g of warm water at about 90 ° C. was added (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.2, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 5 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 530 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
約90℃の温水216.9gにヘプタモリブデン酸アンモニウム72.3gを溶解させた(A液)。また、硝酸ビスマス28.1g、硝酸セリウム14.7g、硝酸カリウム0.35g、硝酸鉄19.2g、硝酸セシウム2.0g、及び硝酸コバルト69.8gを18質量%の硝酸水溶液40.6gに溶解させ、約90℃の温水181.7gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.3に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで3hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、520℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A2]
72.3 g of ammonium heptamolybdate was dissolved in 216.9 g of warm water at about 90 ° C. (solution A). Also, 28.1 g of bismuth nitrate, 14.7 g of cerium nitrate, 0.35 g of potassium nitrate, 19.2 g of iron nitrate, 2.0 g of cesium nitrate, and 69.8 g of cobalt nitrate were dissolved in 40.6 g of 18% by mass nitric acid aqueous solution. Then, 181.7 g of warm water at about 90 ° C. was added (liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.3, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 520 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
約90℃の温水197.2gにヘプタモリブデン酸アンモニウム65.7gを溶解させた(A液)。また、硝酸ビスマス64.5g、硝酸鉄42.4g、硝酸セシウム0.54g、及び硝酸コバルト30.8gを18質量%の硝酸水溶液40.6gに溶解させ、約90℃の温水203.6gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.0に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで3hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、540℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A3]
65.7 g of ammonium heptamolybdate was dissolved in 197.2 g of warm water at about 90 ° C. (solution A). Also, 64.5 g of bismuth nitrate, 42.4 g of iron nitrate, 0.54 g of cesium nitrate, and 30.8 g of cobalt nitrate were dissolved in 40.6 g of an 18% by mass nitric acid aqueous solution, and 203.6 g of hot water at about 90 ° C. was added. (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and then calcined in air at 540 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
約90℃の温水309.9gにヘプタモリブデン酸アンモニウム70.0gとメタバナジン酸アンモニウム5.4gを溶解させた(A液)。また、硝酸ビスマス46.3g、硝酸鉄45.2g、硝酸セシウム0.57g、及び硝酸コバルト32.8gを18質量%の硝酸水溶液38.6gに溶解させ、約90℃の温水170.3gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.5に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで3hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、460℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A4]
70.0 g of ammonium heptamolybdate and 5.4 g of ammonium metavanadate were dissolved in 309.9 g of warm water at about 90 ° C. (solution A). Also, 46.3 g of bismuth nitrate, 45.2 g of iron nitrate, 0.57 g of cesium nitrate, and 32.8 g of cobalt nitrate are dissolved in 38.6 g of 18% by mass nitric acid aqueous solution, and 170.3 g of hot water at about 90 ° C. is added. (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.5, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 3 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 460 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
イオン交換水90.2gと、濃度30質量%の過酸化水素水127.0gとの混合液に、三酸化モリブデン54.3gを入れ、約70℃で攪拌混合し、溶解させて溶液(A液)を得た。また、10質量%の平均粒子径51nmの酸化ビスマス水分散液168.9g、15質量%の平均粒子径22nmの酸化コバルト水分散液63.7g、15質量%の平均粒子径39nmの酸化鉄水分散液66.9g、及び10質量%の平均粒子径20nmの酸化セリウム水分散液84.9g、及び10質量%の水酸化セシウム液4.2gを混合して溶液(B液)を得た。 [Comparative Example A5]
In a mixed solution of 90.2 g of ion-exchanged water and 127.0 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.3 g of molybdenum trioxide is stirred and mixed at about 70 ° C., dissolved, and dissolved (solution A). ) Further, 168.9 g of 10% by mass bismuth oxide aqueous dispersion having an average particle size of 51 nm, 63.7 g of 15% by mass cobalt oxide aqueous dispersion having an average particle size of 22 nm, and 15% by mass of iron oxide water having an average particle size of 39 nm. 66.9 g of the dispersion, 84.9 g of 10% by mass of cerium oxide aqueous dispersion having an average particle diameter of 20 nm, and 4.2 g of 10% by mass of cesium hydroxide solution were mixed to obtain a solution (liquid B).
組成がMo12原子を基準とした原子比としてMo12Bi1.6Ce0.4Fe1.0Co8.0Cs0.4K0.2で表わされる触媒組成物を次のようにして調製した。約50℃の温水1820gにヘプタモリブデン酸アンモニウム364gを溶解させた(A液)。また、硝酸ビスマス133g、硝酸セリウム29.8g、硝酸鉄69.4g、硝酸セシウム13.4g、硝酸カリウム3.46gおよび硝酸コバルト400gを15重量%の硝酸水溶液290gに溶解させた(B液)。A液とB液の両液を約2時間程度撹拌混合して原料スラリーを得た。この原料スラリーを噴霧乾燥し、さらに得られた噴霧乾燥触媒組成物前駆体を200℃で3時間仮焼した。かくして得られた疑似球形粒子状の仮焼触媒組成物前駆体を直径5mm高さ4mmの円柱状に打錠成型し、460℃で3時間焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A6]
A catalyst composition having a composition represented by Mo 12 Bi 1.6 Ce 0.4 Fe 1.0 Co 8.0 Cs 0.4 K 0.2 as an atomic ratio based on Mo12 atoms was prepared as follows. did. 364 g of ammonium heptamolybdate was dissolved in 1820 g of warm water at about 50 ° C. (solution A). Further, 133 g of bismuth nitrate, 29.8 g of cerium nitrate, 69.4 g of iron nitrate, 13.4 g of cesium nitrate, 3.46 g of potassium nitrate and 400 g of cobalt nitrate were dissolved in 290 g of a 15 wt% nitric acid aqueous solution (B solution). Both liquids A and B were stirred and mixed for about 2 hours to obtain a raw material slurry. This raw material slurry was spray-dried, and the obtained spray-dried catalyst composition precursor was calcined at 200 ° C. for 3 hours. The pseudo-spherical calcined catalyst composition precursor thus obtained was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and calcined at 460 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
[実施例A8]
イオン交換水90.7gと、濃度30質量%の過酸化水素水127.8gとの混合液に、三酸化モリブデン54.6gを入れ、約70℃で攪拌混合し、溶解させて溶液(A液)を得た。また、10質量%の平均粒子径51nmの酸化ビスマス水分散液205.3g、15質量%の平均粒子径22nmの酸化コバルト水分散液54.5g、15質量%の平均粒子径39nmの酸化鉄水分散液57.2g、及び10質量%の平均粒子径40nmの酸化ランタン水分散液72.1g、及び10質量%の水酸化セシウム液1.4gを混合して溶液(B液)を得た。 <Acrolein synthesis reaction>
[Example A8]
In a mixed solution of 90.7 g of ion-exchanged water and 127.8 g of hydrogen peroxide solution having a concentration of 30% by mass, 54.6 g of molybdenum trioxide is stirred and mixed at about 70 ° C., dissolved and dissolved (solution A). ) Further, 205.3 g of an aqueous bismuth oxide dispersion having an average particle diameter of 51 nm of 10% by mass, 54.5 g of an aqueous cobalt oxide dispersion having an average particle diameter of 22 nm of 15% by mass, and iron oxide water having an average particle diameter of 39 nm of 15% by mass. A solution (liquid B) was obtained by mixing 57.2 g of the dispersion, 72.1 g of a 10% by mass lanthanum oxide aqueous dispersion having an average particle size of 40 nm, and 1.4 g of a 10% by mass cesium hydroxide solution.
約90℃の温水203.1gにヘプタモリブデン酸アンモニウム67.7gを溶解させた(A液)。また、硝酸ビスマス37.1g、硝酸セリウム22.0g、硝酸鉄51.4g、硝酸セシウム0.19g、及び硝酸コバルト37.4gを18質量%の硝酸水溶液41.9gに溶解させ、約90℃の温水205.7gを添加した(B液)。A液とB液の両液を混合し、アンモニア水を添加し、pHを4.0に調整し、約55℃で約3時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から250℃まで20分で昇温し、250℃で3時間保持し、仮焼成体を得た。得られた仮焼成体を直径5mm高さ4mm、内径2mmのリング状に打錠成型し、空気中で、460℃で5時間本焼成し、触媒を得た。触媒の組成を表1に示し、粉末X線回折の測定結果を表2に示す。 [Comparative Example A7]
67.7 g of ammonium heptamolybdate was dissolved in 203.1 g of warm water at about 90 ° C. (solution A). Further, 37.1 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.4 g of iron nitrate, 0.19 g of cesium nitrate, and 37.4 g of cobalt nitrate were dissolved in 41.9 g of an 18% by mass nitric acid aqueous solution, Warm water 205.7 g was added (Liquid B). Both liquid A and liquid B were mixed, aqueous ammonia was added to adjust the pH to 4.0, and the mixture was stirred and mixed at about 55 ° C. for about 3 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 250 ° C. in 20 minutes and held at 250 ° C. for 3 hours to obtain a provisional fired body. The obtained calcined product was tablet-molded into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm, and was calcined in air at 460 ° C. for 5 hours to obtain a catalyst. The composition of the catalyst is shown in Table 1, and the measurement result of powder X-ray diffraction is shown in Table 2.
[実施例A9]
実施例A2と同じ触媒を使用して1-ブテンからブタジエンを以下のとおりに合成した。直径14mmのジャケット付SUS製反応管に、触媒6.0gを充填し、反応温度360℃で1-ブテン8容量%、酸素12.8容量%、窒素容量79.2%からなる混合ガスを120mL/min(NTP)の流量で通気し、ブタジエン合成反応を行った。反応評価結果を表5に示す。 <Butadiene synthesis reaction>
[Example A9]
Using the same catalyst as Example A2, butadiene was synthesized from 1-butene as follows. A jacketed SUS reaction tube with a diameter of 14 mm was filled with 6.0 g of catalyst, and 120 mL of a mixed gas consisting of 1-butene 8% by volume, oxygen 12.8% by volume, nitrogen volume 79.2% at a reaction temperature of 360 ° C. Aeration was conducted at a flow rate of / min (NTP) to carry out a butadiene synthesis reaction. The reaction evaluation results are shown in Table 5.
比較例A5と同じ触媒を使用して反応管に触媒6.0gを充填し、実施例A9と同じ反応条件で1-ブテンからブタジエンを以下のとおりに合成した。反応評価結果を表5に示す。 [Comparative Example A8]
Using the same catalyst as in Comparative Example A5, 6.0 g of catalyst was charged into the reaction tube, and butadiene was synthesized from 1-butene under the same reaction conditions as in Example A9 as follows. The reaction evaluation results are shown in Table 5.
実施例A1及び比較例A3で得られた触媒のX線回折ピークを図5に示す。また、図5におけるX線回折ピークの2θ=15~30°の範囲の拡大図を図6に、2θ=30~50°の範囲の拡大図を図7に示す。図5及び6から、実施例A1で得られた触媒のX線回折において、少なくとも2θ=18.34°(101)面、28.16°(112)面、33.66°(200)面、46.10°にピークを示し、2θ=33.66°のピーク強度Iaと2θ=34.06°のピーク強度Ibの強度比(Ia/Ib)=3.3であり、実施例A1で得られた触媒においては、disorder相Bi3-xAxFe1Mo2O12の結晶構造が生成したと判断できる。 <X-ray diffraction peaks of the catalysts obtained in Example A1 and Comparative Example A3>
FIG. 5 shows X-ray diffraction peaks of the catalysts obtained in Example A1 and Comparative Example A3. FIG. 6 shows an enlarged view of the range of 2θ = 15 to 30 ° of the X-ray diffraction peak in FIG. 5, and FIG. 7 shows an enlarged view of the range of 2θ = 30 to 50 °. 5 and 6, in the X-ray diffraction of the catalyst obtained in Example A1, at least 2θ = 18.34 ° (101) plane, 28.16 ° (112) plane, 33.66 ° (200) plane, A peak was observed at 46.10 °, and the intensity ratio (Ia / Ib) of the peak intensity Ia at 2θ = 33.66 ° and the peak intensity Ib at 2θ = 34.06 ° was 3.3, which was obtained in Example A1. In the obtained catalyst, it can be judged that the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 was formed.
以下に実施例Bを示して、第2の実施形態をより詳細に説明するが、第2の実施形態は以下に記載の実施例Bによって限定されるものではない。なお、アンモ酸化触媒における酸素原子の原子比は、他の元素の原子価条件により決定されるものであり、実施例及び比較例においては、触媒の組成を表す式中、酸素原子の原子比は省略する。また、アンモ酸化触媒における各元素の組成比は、仕込みの組成比から算出した。
なお、以下の実施例B及び比較例Bにおいて、触媒原料として各種金属の水分散液を用いる場合、酸化ビスマス、酸化鉄及び酸化コバルト水分散液はCIKナノテック株式会社製の水分散液を、酸化ランタン及び酸化セリウム水分散液は多木化学株式会社製の水分散液を使用した。 [Example B]
Example B will be described below to describe the second embodiment in more detail. However, the second embodiment is not limited to Example B described below. The atomic ratio of oxygen atoms in the ammoxidation catalyst is determined by the valence conditions of other elements. In Examples and Comparative Examples, the atomic ratio of oxygen atoms in the formulas representing the composition of the catalyst is Omitted. Further, the composition ratio of each element in the ammoxidation catalyst was calculated from the composition ratio of preparation.
In Examples B and Comparative Examples B below, when an aqueous dispersion of various metals is used as a catalyst raw material, bismuth oxide, iron oxide and cobalt oxide aqueous dispersions are obtained by oxidizing an aqueous dispersion manufactured by CIK Nanotech Co., Ltd. As the lanthanum and cerium oxide aqueous dispersion, an aqueous dispersion manufactured by Taki Chemical Co., Ltd. was used.
平均粒子径は、以下の式に従って計算により求めた。
平均粒子径[nm]=6000/(表面積[m2/g]×真密度(8.99g/cm3) <Measurement of average particle diameter>
The average particle size was obtained by calculation according to the following formula.
Average particle diameter [nm] = 6000 / (surface area [m 2 / g] × true density (8.99 g / cm 3 )
AS ONE製のpH METER KR5Eを用いて測定した。 <Measurement of pH>
It measured using pH METER KR5E made from AS ONE.
XRDの測定は、National Institute of Standards & Technologyが標準参照物質660として定めるところのLaB6化合物の(111)面、(200)面を測定し、それぞれの値を37.441°、43.506°となるように規準化した。
XRDの装置としては、ブルカー・D8 ADVANCEを用いた。XRDの測定条件は、X線出力:40kV-40mA、発散スリット(DS):0.3°、Step幅:0.02°/step、計数Time:2.0sec、測定範囲:2θ=5°~60°とした。 <Measurement of X-ray diffraction angle>
XRD is measured by measuring the (111) plane and (200) plane of the LaB 6 compound as defined by National Institute of Standards & Technology as the standard reference material 660, and the respective values are 37.441 °, 43.506 °. It was standardized to become.
Bruker D8 ADVANCE was used as the XRD apparatus. The XRD measurement conditions are: X-ray output: 40 kV-40 mA, divergent slit (DS): 0.3 °, step width: 0.02 ° / step, counting time: 2.0 sec, measurement range: 2θ = 5 ° to The angle was 60 °.
10メッシュの金網を1cm間隔で12枚内蔵した内径25mmのバイコールガラス製流動層反応管に40~60gの触媒をとり、反応温度430℃、反応圧力常圧下に、混合ガス(プロピレン又はイソブチレン:アンモニア:酸素:ヘリウムの容積比が1:1.2:1.85:7.06)を毎秒3.64cc(NTP換算)の流速で通過させた。 <Reaction evaluation conditions for ammoxidation reaction>
40 to 60 g of catalyst is placed in a 25 mm inner diameter Vycor glass fluidized bed reaction tube containing 12 10-mesh wire meshes at 1 cm intervals, and a mixed gas (propylene or isobutylene: ammonia at a reaction temperature of 430 ° C. and a normal pressure of reaction). : Oxygen: helium volume ratio of 1: 1.2: 1.85: 7.06) was passed at a flow rate of 3.64 cc (NTP conversion) per second.
反応成績を表すために用いた転化率、選択率、収率は次式で定義される。
転化率=(反応した原料のモル数/供給した原料のモル数)×100
選択率=(生成した化合物のモル数/反応した原料のモル数)×100
収率=(生成した化合物のモル数/供給した原料のモル数)×100 <Conversion rate, selectivity, yield>
The conversion rate, selectivity, and yield used to express the reaction results are defined by the following equations.
Conversion rate = (number of moles of reacted raw material / number of moles of supplied raw material) × 100
Selectivity = (number of moles of compound produced / number of moles of reacted raw material) × 100
Yield = (Mole number of produced compound / Mole number of supplied raw material) × 100
接触時間は次式で定義される。
接触時間(sec・g/cc)=(W/F)×273/(273+T)×P/0.10 式中、Wは触媒の量(g)、Fは標準状態(0℃、1atm)での原料混合ガス流量(Ncc/sec)、Tは反応温度(℃)、そしてPは反応圧力(MPa)を示す。 <Contact time>
The contact time is defined by the following equation.
Contact time (sec · g / cc) = (W / F) × 273 / (273 + T) × P / 0.10 where W is the amount of catalyst (g), and F is the standard state (0 ° C., 1 atm). The raw material mixed gas flow rate (Ncc / sec), T is the reaction temperature (° C.), and P is the reaction pressure (MPa).
還元性評価は、触媒の耐還元性を加速的に評価するために実施した。酸素を含まないガス雰囲気の還元処理で触媒が還元され、反応評価条件に戻すことで触媒が再酸化される。これを繰り返すことで加速的な触媒の耐還元性を評価することができる。
430℃の温度で、2容量%、のプロピレン、イソブチレン、イソブタノール及又はt-ブチルアルコールとヘリウム98容量%の混合ガスを毎秒3.64cc(NTP換算)の流速で5min流通させることで還元処理を実施し、その後、上述の反応評価条件に戻し、5min流通させた。これを1セットとし、合計100セット実施し、反応評価を行った。さらに100セット実施し、反応評価を行い、耐還元性を評価した。 <Reducibility evaluation>
The reduction evaluation was performed in order to accelerate the reduction resistance of the catalyst. The catalyst is reduced by the reduction treatment in the gas atmosphere not containing oxygen, and the catalyst is reoxidized by returning to the reaction evaluation condition. By repeating this, the reduction resistance of the accelerated catalyst can be evaluated.
Reduction treatment by flowing 2 volume% of propylene, isobutylene, isobutanol and a mixed gas of t-butyl alcohol and helium 98 volume% at a temperature of 430 ° C. for 5 minutes at a flow rate of 3.64 cc (NTP conversion) per second. After that, it was returned to the above-mentioned reaction evaluation conditions and allowed to flow for 5 minutes. This was set as one set, and a total of 100 sets were carried out to evaluate the reaction. Furthermore, 100 sets were implemented, reaction evaluation was performed, and reduction resistance was evaluated.
La 1.14Å
Ce 1.07Å
Pr 1.06Å
Ca 1.03Å
Pb 1.24Å
V 0.56Å Moreover, the ionic radius of the element A used in Example B and Comparative Example B is as follows.
La 1.14Å
Ce 1.07mm
Pr 1.06mm
Ca 1.03Å
Pb 1.24mm
V 0.56mm
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水211.0gにヘプタモリブデン酸アンモニウム70.3gを溶解させた(A液)。また、硝酸ビスマス38.6g、硝酸ランタン22.9g、硝酸鉄42.7g、硝酸セシウム0.51g、及び硝酸コバルト31.4gを18質量%の硝酸水溶液36.4gに溶解させ、約90℃の温水148.1gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを4.1に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、260℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.3(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B1]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
70.3 g of ammonium heptamolybdate was dissolved in 211.0 g of hot water at about 90 ° C. (solution A). Also, 38.6 g of bismuth nitrate, 22.9 g of lanthanum nitrate, 42.7 g of iron nitrate, 0.51 g of cesium nitrate, and 31.4 g of cobalt nitrate were dissolved in 36.4 g of 18% by mass nitric acid aqueous solution, 148.1 g of warm water was added (solution B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 55 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 4.3 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水207.8gにヘプタモリブデン酸アンモニウム69.3gを溶解させた(A液)。また、硝酸ビスマス41.1g、硝酸セリウム19.7g、硝酸鉄44.7g、硝酸セシウム0.50g、及び硝酸コバルト32.5gを18質量%の硝酸水溶液40.9gに溶解させ、約90℃の温水194.7gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.3に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.2(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B2]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
69.3 g of ammonium heptamolybdate was dissolved in 207.8 g of warm water at about 90 ° C. (solution A). Further, 41.1 g of bismuth nitrate, 19.7 g of cerium nitrate, 44.7 g of iron nitrate, 0.50 g of cesium nitrate, and 32.5 g of cobalt nitrate were dissolved in 40.9 g of an 18% by mass nitric acid aqueous solution, 194.7 g of warm water was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.3, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 55 g of catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and ammoxidation reaction of propylene was performed at a contact time of 4.2 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水209.1gにヘプタモリブデン酸アンモニウム69.7gを溶解させた(A液)。また、硝酸ビスマス44.6g、硝酸プラセオジム17.0g、硝酸鉄31.8g、硝酸セシウム0.57g、及び硝酸コバルト38.4gを18質量%の硝酸水溶液40.2gに溶解させ、約90℃の温水188.8gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、270℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.4(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B3]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
69.7 g of ammonium heptamolybdate was dissolved in 209.1 g of warm water at about 90 ° C. (solution A). Further, 44.6 g of bismuth nitrate, 17.0 g of praseodymium nitrate, 31.8 g of iron nitrate, 0.57 g of cesium nitrate, and 38.4 g of cobalt nitrate were dissolved in 40.2 g of an 18% by mass nitric acid aqueous solution, 188.8 g of warm water was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 270 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 57 g of catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of propylene was performed at a contact time of 4.4 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水223.4gにヘプタモリブデン酸アンモニウム74.5gを溶解させた(A液)。また、硝酸ビスマス20.4g、硝酸ランタン30.3g、硝酸鉄45.2g、硝酸セシウム0.54g、硝酸カルシウム6.6g、及び硝酸コバルト32.9gを18質量%の硝酸水溶液34.3gに溶解させ、約90℃の温水114.4gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、240℃まで1時間かけて昇温し、4時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、580℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.5(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B4]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
74.5 g of ammonium heptamolybdate was dissolved in 223.4 g of warm water at about 90 ° C. (solution A). Also, 20.4 g of bismuth nitrate, 30.3 g of lanthanum nitrate, 45.2 g of iron nitrate, 0.54 g of cesium nitrate, 6.6 g of calcium nitrate, and 32.9 g of cobalt nitrate were dissolved in 34.3 g of 18% by mass nitric acid aqueous solution. Then, 114.4 g of warm water at about 90 ° C. was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 240 ° C. over 1 hour and held for 4 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 580 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As an evaluation of the catalyst reaction, 57 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 4.5 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水202.0gにヘプタモリブデン酸アンモニウム67.3gを溶解させた(A液)。また、硝酸ビスマス21.5g、硝酸セリウム24.6g、硝酸鉄42.2g、硝酸セシウム0.74g、硝酸鉛8.4g、及び硝酸コバルト47.3gを18質量%の硝酸水溶液39.4gに溶解させ、約90℃の温水182.0gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.6(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B5]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
67.3 g of ammonium heptamolybdate was dissolved in 202.0 g of hot water at about 90 ° C. (solution A). Also, 21.5 g of bismuth nitrate, 24.6 g of cerium nitrate, 42.2 g of iron nitrate, 0.74 g of cesium nitrate, 8.4 g of lead nitrate, and 47.3 g of cobalt nitrate were dissolved in 39.4 g of 18% by mass nitric acid aqueous solution. Then, 182.0 g of warm water at about 90 ° C. was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As an evaluation of the catalyst reaction, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of propylene was performed at a contact time of 4.6 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水211.8gにヘプタモリブデン酸アンモニウム70.6gを溶解させた(A液)。また、硝酸ビスマス37.1g、硝酸セリウム21.5g、硝酸鉄41.5g、硝酸ルビジウム0.63g、硝酸マグネシウム10.2g、硝酸コバルト19.5g及び硝酸ニッケル9.8gを18質量%の硝酸水溶液41.3gに溶解させ、約90℃の温水193.1gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.7(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B6]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
70.6 g of ammonium heptamolybdate was dissolved in 211.8 g of warm water at about 90 ° C. (solution A). Also, an aqueous 18% by mass nitric acid solution containing 37.1 g of bismuth nitrate, 21.5 g of cerium nitrate, 41.5 g of iron nitrate, 0.63 g of rubidium nitrate, 10.2 g of magnesium nitrate, 19.5 g of cobalt nitrate and 9.8 g of nickel nitrate It was dissolved in 41.3 g, and 193.1 g of hot water at about 90 ° C. was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 57 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 4.7 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水210.8gにヘプタモリブデン酸アンモニウム70.3gを溶解させた(A液)。また、硝酸ビスマス27.3g、硝酸セリウム14.3g、硝酸鉄20.0g、硝酸ルビジウム1.94g、硝酸カリウム0.67g、硝酸亜鉛4.9g及び硝酸コバルト72.7gを18質量%の硝酸水溶液40.5gに溶解させ、約90℃の温水186.0gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間4.6(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Example B7]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
70.3 g of ammonium heptamolybdate was dissolved in 210.8 g of warm water at about 90 ° C. (solution A). Further, 27.3 g of bismuth nitrate, 14.3 g of cerium nitrate, 20.0 g of iron nitrate, 1.94 g of rubidium nitrate, 0.67 g of potassium nitrate, 4.9 g of zinc nitrate, and 72.7 g of cobalt nitrate were added to a 40% by mass nitric acid
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As an evaluation of the catalyst reaction, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of propylene was performed at a contact time of 4.6 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水203.4gにヘプタモリブデン酸アンモニウム67.8gを溶解させた(A液)。また、硝酸ビスマス61.9、硝酸鉄46.3g、硝酸セシウム0.49g、及び硝酸コバルト26.2gを18質量%の硝酸水溶液40.4gに溶解させ、約90℃の温水195.7gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを4.1に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、260℃まで1時間かけて昇温し、4時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.6(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Comparative Example B1]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
67.8 g of ammonium heptamolybdate was dissolved in 203.4 g of warm water at about 90 ° C. (solution A). Also, 61.9 g of bismuth nitrate, 46.3 g of iron nitrate, 0.49 g of cesium nitrate, and 26.2 g of cobalt nitrate were dissolved in 40.4 g of an 18% by mass nitric acid aqueous solution, and 195.7 g of hot water at about 90 ° C. was added. (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 4 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 55 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 5.6 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水252.6gにヘプタモリブデン酸アンモニウム84.2gを溶解させた(A液)。また、硝酸ビスマス5.8g、硝酸セリウム3.4g、硝酸鉄24.0g、硝酸ルビジウム0.70g、硝酸マグネシウム26.4g及び硝酸ニッケル75.6gを18質量%の硝酸水溶液41.8gに溶解させ、約90℃の温水150.8gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.4(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Comparative Example B2]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
84.2 g of ammonium heptamolybdate was dissolved in 252.6 g of warm water at about 90 ° C. (solution A). Also, 5.8 g of bismuth nitrate, 3.4 g of cerium nitrate, 24.0 g of iron nitrate, 0.70 g of rubidium nitrate, 26.4 g of magnesium nitrate and 75.6 g of nickel nitrate were dissolved in 41.8 g of 18% by mass nitric acid aqueous solution. 150.8 g of warm water of about 90 ° C. was added (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As an evaluation of the reaction of the catalyst, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of propylene was performed at a contact time of 5.4 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水249.9gにヘプタモリブデン酸アンモニウム83.3gを溶解させた(A液)。また、硝酸ビスマス8.6g、硝酸セリウム15.2g、硝酸鉄26.9g、硝酸ルビジウム0.23g、硝酸マグネシウム20.1g、硝酸コバルト34.5g、硝酸カリウム0.36g及び硝酸ニッケル23.0gを18質量%の硝酸水溶液40.9gに溶解させ、約90℃の温水148.1gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを3.6に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、260℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.3(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Comparative Example B3]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
83.3 g of ammonium heptamolybdate was dissolved in 249.9 g of warm water at about 90 ° C. (solution A). Also, 8.6 g of bismuth nitrate, 15.2 g of cerium nitrate, 26.9 g of iron nitrate, 0.23 g of rubidium nitrate, 20.1 g of magnesium nitrate, 34.5 g of cobalt nitrate, 0.36 g of potassium nitrate and 23.0 g of nickel nitrate were added. It melt | dissolved in 40.9g of nitric acid aqueous solution of a mass%, and the hot water 148.1g of about 90 degreeC was added (B liquid).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 3.6, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 260 ° C. over 1 hour, and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As an evaluation of the reaction of the catalyst, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of propylene was performed at a contact time of 5.3 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
シリカ1次粒子の平均直径が44nmのSiO2を26質量%含む40質量%のシリカゾル125.0gと、シリカ1次粒子の平均直径が12nmのSiO2を30質量%含む34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。
約90℃の温水216.3gにヘプタモリブデン酸アンモニウム72.1gとメタバナジン酸アンモニウム5.2gを溶解させた(A液)。また、硝酸ビスマス44.4、硝酸鉄43.8g、硝酸セシウム0.46g、及び硝酸コバルト31.8gを18質量%の硝酸水溶液38.3gに溶解させ、約90℃の温水161.9gを添加した(B液)。
上記シリカ原料とA液とB液の両液を混合し、アンモニア水を添加し、pHを4.1に調整し、約55℃で約4時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入り口温度250℃、出口温度約140℃で噴霧乾燥し、酸化物触媒前駆体を得た。得られた酸化物触媒前駆体を、空気中で100℃から200℃まで2hかけて昇温した後、250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、580℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.9(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Comparative Example B4]
125.0 g of 40% by mass silica sol containing 26% by mass of SiO 2 having an average diameter of 44 nm of silica primary particles and 34% by mass of aqueous silica sol containing 30% by mass of SiO 2 having an average diameter of 12 nm of silica primary particles 147.1 g and 61.3 g of water were mixed to obtain a silica raw material of 30% by mass.
72.1 g of ammonium heptamolybdate and 5.2 g of ammonium metavanadate were dissolved in 216.3 g of warm water at about 90 ° C. (solution A). Also, 44.4 g of bismuth nitrate, 43.8 g of iron nitrate, 0.46 g of cesium nitrate, and 31.8 g of cobalt nitrate are dissolved in 38.3 g of an 18% by mass nitric acid aqueous solution, and 161.9 g of hot water at about 90 ° C. is added. (Liquid B).
The silica raw material, both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was stirred and mixed at about 55 ° C. for about 4 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain an oxide catalyst precursor. The obtained oxide catalyst precursor was heated in air from 100 ° C. to 200 ° C. over 2 hours, then heated to 250 ° C. over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 580 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 55 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 5.9 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
実施例B1と同じ酸化物触媒前駆体を空気中で250℃まで1時間かけて昇温し、3時間保持して仮焼成体を得た。得られた仮焼成体を空気中で、570℃で3時間本焼成し、触媒を得た。触媒の組成を表6に示し、粉末X線回折の測定結果を表7に示す。
触媒の反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.8(sec・g/cc)でプロピレンのアンモ酸化反応を行った。反応評価結果を表8に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表8に示す。 [Comparative Example B5]
The same oxide catalyst precursor as in Example B1 was heated to 250 ° C. in air over 1 hour and held for 3 hours to obtain a pre-fired body. The obtained calcined product was calcined in the air at 570 ° C. for 3 hours to obtain a catalyst. The composition of the catalyst is shown in Table 6, and the measurement result of powder X-ray diffraction is shown in Table 7.
As a catalyst reaction evaluation, 55 g of catalyst was packed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and propylene ammoxidation reaction was performed at a contact time of 5.8 (sec · g / cc). Table 8 shows the reaction evaluation results. Table 8 also shows the results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
実施例B1の触媒を用い、反応評価として、触媒57gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間5.4(sec・g/cc)でイソブチレンのアンモ酸化反応を行った。反応評価結果を表9に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表9に示す。 [Example B8]
Using the catalyst of Example B1, as a reaction evaluation, 57 g of the catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of isobutylene was performed at a contact time of 5.4 (sec · g / cc). . Table 9 shows the reaction evaluation results. Table 9 also shows the results of reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
比較例B5と同じ触媒を用い、反応評価として、触媒55gを内径25mmのバイコールガラス製流動層反応管に充填し、接触時間6.0(sec・g/cc)でイソブチレンのアンモ酸化反応を行った。反応評価結果を表9に示す。また、加速還元評価を100セット及び200セット実施した後の反応評価結果も、同様に表9に示す。 [Comparative Example B6]
Using the same catalyst as in Comparative Example B5, as a reaction evaluation, 55 g of catalyst was filled in a fluidized bed reaction tube made of Vycor glass having an inner diameter of 25 mm, and an ammoxidation reaction of isobutylene was performed at a contact time of 6.0 (sec · g / cc). It was. Table 9 shows the reaction evaluation results. Table 9 also shows the results of reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation were performed.
実施例B1及び比較例B1で得られた触媒のX線回折ピークを図9に示す。また、図9におけるX線回折ピークの2θ=15~30°の範囲の拡大図を図10に、2θ=30~50°の範囲の拡大図を図11に示す。図9及び10から、実施例B1で得られた触媒のX線回折において、少なくとも2θ=18.28°(101)面、28.16°(112)面、33.60°(200)面、46.00°にピークを示し、2θ=33.60°のピーク強度Iaと2θ=34.06°のピーク強度Ibの強度比(Ia/Ib)=3.3であり、実施例B1で得られた触媒においては、disorder相Bi3-xAxFe1Mo2O12の結晶構造が生成したと判断できる。 <X-ray diffraction peaks of the catalysts obtained in Example B1 and Comparative Example B1>
FIG. 9 shows the X-ray diffraction peaks of the catalysts obtained in Example B1 and Comparative Example B1. Further, FIG. 10 shows an enlarged view of the range of 2θ = 15 to 30 ° of the X-ray diffraction peak in FIG. 9, and FIG. 11 shows an enlarged view of the range of 2θ = 30 to 50 °. 9 and 10, in the X-ray diffraction of the catalyst obtained in Example B1, at least 2θ = 18.28 ° (101) plane, 28.16 ° (112) plane, 33.60 ° (200) plane, A peak was observed at 46.00 °, and the intensity ratio (Ia / Ib) = 3.3 of the peak intensity Ia at 2θ = 33.60 ° and the peak intensity Ib at 2θ = 34.06 ° was obtained in Example B1. is in the catalyst, it can be determined that the crystal structure of the disorder phase Bi 3-x a x Fe 1 Mo 2 O 12 was produced.
実施例B1と比較例B1で得られた触媒のX線回折を比較すると、実施例B1で得られた触媒の18.34°(101)面のピークについては、比較例B1で得られた触媒は18.10°(310)面と18.45°(111)面にピーク分裂が観測され、実施例B1で得られた触媒の28.20°±0.2°(112)面のピークについては、比較例B1で得られた触媒は28.00°(221)面と28.35°(42-1)面にピーク分裂が観測され、実施例B1で得られた触媒の33.65°±0.2°(200)面のピークについては、比較例B1で得られた触媒は33.30°(600)面と34.10°(202)面にピーク分裂が観測され、実施例B1で得られた触媒の46.15°±0.2°(204)面のピークについては、比較例B1で得られた触媒は45.90°(640)面と46.45°(242)面にピーク分裂が観測された。2θ=33.60°のピーク強度Iaと2θ=34.06°のピーク強度Ibの強度比(Ia/Ib)=1.0であり、実施例B1で得られた触媒においては、disorder相Bi3-xAxFe1Mo2O12の結晶構造が生成したと判断できる。これに対して、比較例B1で得られた触媒においては、disorder相Bi3-xAxFe1Mo2O12ではなく、order相が生成していると判断できる。 On the other hand, in the X-ray diffraction of the catalyst obtained in Comparative Example B1, 18.30 ° ± 0.05 ° (101) plane, 28.20 ° ± 0.05 ° (112) plane, 33.65 ° ± No peaks were observed on the 0.05 ° (200) plane and 46.15 ° ± 0.05 ° (204) plane. That is, in the catalyst obtained in Comparative Example B1, it can be determined that the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 did not generate.
When the X-ray diffraction of the catalyst obtained in Example B1 and Comparative Example B1 is compared, the peak obtained at 18.34 ° (101) plane of the catalyst obtained in Example B1 is the catalyst obtained in Comparative Example B1. Shows peak splitting at 18.10 ° (310) plane and 18.45 ° (111) plane, and the peak of 28.20 ° ± 0.2 ° (112) plane of the catalyst obtained in Example B1. In the catalyst obtained in Comparative Example B1, peak splitting was observed on the 28.00 ° (221) plane and 28.35 ° (42-1) plane, and the catalyst obtained in Example B1 was 33.65 °. Regarding the peak of ± 0.2 ° (200) plane, peak splitting was observed on the 33.30 ° (600) plane and 34.10 ° (202) plane of the catalyst obtained in Comparative Example B1, and Example B1 The peak of the 46.15 ° ± 0.2 ° (204) plane of the catalyst obtained in the above is compared. Catalyst obtained in B1 peak splits into 45.90 ° (640) plane and 46.45 ° (242) plane was observed. The intensity ratio (Ia / Ib) = 1.0 of the peak intensity Ia of 2θ = 33.60 ° and the peak intensity Ib of 2θ = 34.06 ° is 1.0, and in the catalyst obtained in Example B1, the disorder phase Bi It can be judged that the crystal structure of 3-x A x Fe 1 Mo 2 O 12 was formed. In contrast, in the catalyst obtained in Comparative Example B1, disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 instead, it can be determined that the order phase is generated.
転化率(%)=(反応したオレフィン及び/又はアルコールのモル数/供給したオレフィン及び/又はアルコールのモル数)×100
選択率(%)=(生成した不飽和アルデヒドのモル数/反応したオレフィン及び/又はアルコールのモル数)×100
収率(%)=(生成した不飽和アルデヒドのモル数/供給したオレフィン及び/又はアルコールのモル数)×100 In Example C and Comparative Example C, the conversion rate, selectivity, and yield used to represent the reaction results are defined by the following equations. The “number of moles of raw material” in the formula is the number of moles of olefin and / or alcohol.
Conversion (%) = (number of moles of reacted olefin and / or alcohol / number of moles of olefin and / or alcohol fed) × 100
Selectivity (%) = (number of moles of unsaturated aldehyde produced / number of moles of reacted olefin and / or alcohol) × 100
Yield (%) = (number of moles of unsaturated aldehyde produced / number of moles of olefin and / or alcohol fed) × 100
シリカ1次粒子の平均粒径が44nmのSiO2を26質量%含む、濃度40質量%のシリカゾル125.0gと、シリカ1次粒子の平均粒径が12nmのSiO2を30質量%含む、濃度34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。 [Example C1]
125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
実施例C1と同じ酸化物触媒40gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/8.8/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量725cm2/min(NTP換算)で供給し、反応温度430℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C2]
Using 40 g of the same oxide catalyst as in Example C1, the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 8.8 / balanced raw material mixed gas (isobutylene concentration = 8 vol%) at a flow rate of 725 cm 2 / The methacrolein synthesis reaction was performed under the conditions of a reaction temperature of 430 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
実施例C1と同じ酸化物触媒30gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/9.4/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量794cm2/min(NTP換算)で供給し、反応温度440℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C3]
30 g of the same oxide catalyst as in Example C1 was used, and the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 9.4 / balanced raw material mixed gas (isobutylene concentration = 8% by volume) at a flow rate of 794 cm 2 / The methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
実施例C1と同じ酸化物触媒40gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/7.9/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量595cm2/min(NTP換算)で供給し、反応温度440℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C4]
Using 40 g of the same oxide catalyst as in Example C1, the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 7.9 / balanced raw material mixed gas (isobutylene concentration = 8% by volume) at a flow rate of 595 cm 2 / The methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
実施例C1と同じ酸化物触媒40gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/9.5/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量625cm2/min(NTP換算)で供給し、反応温度440℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C5]
40 g of the same oxide catalyst as in Example C1 was used, and the raw material mixed gas (isobutylene concentration = 8% by volume) having a molar ratio composition of the raw material mixed gas of isobutylene / air / helium = 1 / 9.5 / balance was 625 cm 2 / The methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
実施例C1と同じ酸化物触媒35gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/8.8/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量595cm2/min(NTP換算)で供給し、反応温度460℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C6]
Using 35 g of the same oxide catalyst as in Example C1, the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 8.8 / balanced raw material mixed gas (isobutylene concentration = 8% by volume) at a flow rate of 595 cm 2 / The methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 460 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
実施例C1と同じ酸化物触媒40gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/8.1/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量595cm2/min(NTP換算)で供給し、反応温度400℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C7]
40 g of the same oxide catalyst as in Example C1 was used, and the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 8.1 / balanced raw material mixed gas (isobutylene concentration = 8 vol%) at a flow rate of 595 cm 2 / min. (Nequivalent to NTP), and methacrolein synthesis reaction was performed under the conditions of a reaction temperature of 400 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
シリカ1次粒子の平均粒径が44nmのSiO2を26質量%含む、濃度40質量%のシリカゾル125.0gと、シリカ1次粒子の平均粒径が12nmのSiO2を30質量%含む、濃度34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。 [Example C8]
125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
シリカ1次粒子の平均粒径が44nmのSiO2を26質量%含む、濃度40質量%のシリカゾル125.0gと、シリカ1次粒子の平均粒径が12nmのSiO2を30質量%含む、濃度34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。 [Example C9]
125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
実施例C1と同じ酸化物触媒40gを用い、原料混合ガスのモル比組成をイソブチレン/空気/ヘリウム=1/10.2/バランスの原料混合ガス(イソブチレン濃度=8体積%)を流量595cm2/min(NTP換算)で供給し、反応温度440℃、反応圧力0.05MPaの条件でメタクロレイン合成反応を行った。このときの出口酸素濃度、触媒と混合ガスの接触時間、反応評価結果を表11に示す。 [Example C10]
40 g of the same oxide catalyst as in Example C1 was used, and the molar ratio composition of the raw material mixed gas was isobutylene / air / helium = 1 / 10.2 / balanced raw material mixed gas (isobutylene concentration = 8 vol%) at a flow rate of 595 cm 2 / The methacrolein synthesis reaction was carried out under the conditions of a reaction temperature of 440 ° C. and a reaction pressure of 0.05 MPa. Table 11 shows the outlet oxygen concentration, the contact time between the catalyst and the mixed gas, and the reaction evaluation results.
シリカ1次粒子の平均粒径が44nmのSiO2を26質量%含む、濃度40質量%のシリカゾル125.0gと、シリカ1次粒子の平均粒径が12nmのSiO2を30質量%含む、濃度34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。 [Comparative Example C1]
125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
シリカ1次粒子の平均粒径が44nmのSiO2を26質量%含む、濃度40質量%のシリカゾル125.0gと、シリカ1次粒子の平均粒径が12nmのSiO2を30質量%含む、濃度34質量%の水性シリカゾル147.1gと、水61.3gを混合して30質量%のシリカ原料を得た。 [Comparative Example C2]
125.0 g of silica sol having a concentration of 40% by mass of SiO 2 having an average particle size of 44 nm of silica primary particles and 30% by mass of SiO 2 having an average particle size of 12 nm of silica primary particles. 147.1 g of an aqueous silica sol of 34% by mass and 61.3 g of water were mixed to obtain a 30% by mass silica raw material.
酸化物触媒について、X線回折(XRD)でX線回折角2θ=5°~60°の範囲を測定すると、CoとMoからなる複合酸化物の(002)面のX線回折角(2θ)に起因するピークが26.46°±0.02°に示される。このCoとMoの複合酸化物に2価の鉄Feが固溶して複合すると、Co2+とFe2+とのイオン半径の違いによってこのピークのシフトが起こる。2価のFeが固溶して複合化した構造となるために、CoとMoと2価のFeを含む複合酸化物に起因するピークは、26.46°ではなくシフト値をα°として、26.46°-α°(0<α)に現示される。26.30~26.40の範囲にピークがあれば、Co2+-Fe2+-Mo-Oの3成分の結晶が生成したと判断する。 <Measurement of powder X-ray diffraction (XRD)>
With respect to the oxide catalyst, the X-ray diffraction angle (2RD) of the (002) plane of the composite oxide composed of Co and Mo is measured by measuring the X-ray diffraction angle 2θ = 5 ° -60 ° by X-ray diffraction (XRD). The peak due to is shown at 26.46 ° ± 0.02 °. When divalent iron Fe is dissolved and combined in this Co and Mo composite oxide, this peak shift occurs due to the difference in ionic radius between Co 2+ and Fe 2+ . Since the divalent Fe has a solid solution and a composite structure, the peak due to the composite oxide containing Co, Mo and divalent Fe is not 26.46 °, but the shift value is α °. Presented at 26.46 ° -α ° (0 <α). If there is a peak in the range of 26.30 to 26.40, it is determined that a three-component crystal of Co 2+ —Fe 2+ —Mo—O was formed.
実施例C1及び比較例C2で得られた触媒のX線回折ピークを図16に示す。図16から、実施例C1で得られた触媒のX線回折において、少なくとも2θ=18.32°(101)面、28.18°(112)面、33.66°(200)面、46.12°にピークを示し、2θ=33.66°のピーク強度Iaと2θ=34.06°のピーク強度Ibの強度比(Ia/Ib)=3.2であり、実施例C1で得られた触媒においては、disorder相Bi3-xAxFe1Mo2O12の結晶構造が生成したと判断できる。 <X-ray diffraction peaks of the catalysts obtained in Example C1 and Comparative Example C2>
FIG. 16 shows the X-ray diffraction peaks of the catalysts obtained in Example C1 and Comparative Example C2. From FIG. 16, in the X-ray diffraction of the catalyst obtained in Example C1, at least 2θ = 18.32 ° (101) plane, 28.18 ° (112) plane, 33.66 ° (200) plane, 46. A peak was observed at 12 °, the intensity ratio (Ia / Ib) of the peak intensity Ia at 2θ = 33.66 ° and the peak intensity Ib at 2θ = 34.06 ° (3.2), which was obtained in Example C1. In the catalyst, it can be judged that the crystal structure of the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 was formed.
Claims (13)
- オレフィン及び/又はアルコールから、不飽和アルデヒド、ジオレフィン、又は不飽和ニトリルを製造する際に用いられる酸化物触媒であって、下記(1)~(3)を満たす酸化物触媒;
(1)モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含有し、
(2)前記モリブデン12原子に対する、前記ビスマスの原子比aが1≦a≦5であり、前記鉄の原子比bが1.5≦b≦6であり、前記元素Aの原子比cが1≦c≦5であり、前記コバルトの原子比dが1≦d≦8であり、
(3)前記モリブデン、前記ビスマス、前記鉄、及び前記元素Aを含む結晶系からなるdisorder相を含む。 An oxide catalyst used for producing an unsaturated aldehyde, diolefin, or unsaturated nitrile from an olefin and / or an alcohol, the oxide catalyst satisfying the following (1) to (3):
(1) Contains molybdenum, bismuth, iron, cobalt, and element A (except for potassium, cesium, and rubidium) having an ionic radius greater than 0.96 、.
(2) The atomic ratio a of the bismuth with respect to 12 atoms of molybdenum is 1 ≦ a ≦ 5, the atomic ratio b of the iron is 1.5 ≦ b ≦ 6, and the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of cobalt is 1 ≦ d ≦ 8,
(3) It includes a disorder phase composed of a crystal system containing the molybdenum, the bismuth, the iron, and the element A. - X線回折における回折角(2θ)が、18.30°±0.2°、28.20°±0.2°、33.65°±0.2°、及び46.15°±0.2°の範囲に単一ピークを有し、且つ、
2θ=33.65°±0.2°のピークaの強度(Ia)と、2θ=34.10°±0.2°のピークbの強度(Ib)との強度比(Ia/Ib)が2.0以上である、請求項1に記載の酸化物触媒。 The diffraction angles (2θ) in X-ray diffraction are 18.30 ° ± 0.2 °, 28.20 ° ± 0.2 °, 33.65 ° ± 0.2 °, and 46.15 ° ± 0.2. Has a single peak in the range of °, and
The intensity ratio (Ia / Ib) between the intensity (Ia) of peak a at 2θ = 33.65 ° ± 0.2 ° and the intensity (Ib) of peak b at 2θ = 34.10 ° ± 0.2 ° The oxide catalyst of Claim 1 which is 2.0 or more. - 下記組成式(1)で表される組成を有する、請求項1又は2に記載の酸化物触媒。
Mo12BiaFebAcCodBeCfOg (1)
(式中、Moはモリブデンであり、Biはビスマスであり、Feは鉄であり、元素Aはイオン半径が0.96Åよりも大きな元素(ただし、カリウム、セシウム及びルビジウムを除く)であり、Coはコバルトであり、元素Bはマグネシウム、亜鉛、銅、ニッケル、マンガン、クロム、及び錫からなる群より選ばれる少なくとも1種の元素であり、元素Cはカリウム、セシウム、及びルビジウムからなる群より選ばれる少なくとも1種の元素であり、a~gは、Mo12原子に対する各元素の原子比であり、Biの原子比aは1≦a≦5であり、Feの原子比bは1.5≦b≦6であり、元素Aの原子比cは1≦c≦5であり、Coの原子比dは1≦d≦8であり、元素Bの原子比eは0≦e<3であり、元素Cの原子比fは0≦f≦2であり、Fe/Coの比は0.8≦b/dであり、gは酸素以外の構成元素の原子価によって決まる酸素の原子数である。) The oxide catalyst of Claim 1 or 2 which has a composition represented by the following compositional formula (1).
Mo 12 Bi a Fe b A c Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius larger than 0.96 ((except potassium, cesium and rubidium), Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1 ≦ a ≦ 5, and Fe atomic ratio b is 1.5 ≦ b. ≦ 6, the atomic ratio c of the element A is 1 ≦ c ≦ 5, the atomic ratio d of Co is 1 ≦ d ≦ 8, the atomic ratio e of the element B is 0 ≦ e <3, The atomic ratio f of C is 0 ≦ f ≦ 2. , The ratio of Fe / Co is 0.8 ≦ b / d, g is the number of oxygen atoms determined by the valency of the constituent elements other than oxygen.) - 担体として、シリカ、アルミナ、チタニア、及びジルコニアからなる群より選ばれる少なくとも1種をさらに含む、請求項1~3のいずれか1項に記載の酸化物触媒。 The oxide catalyst according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of silica, alumina, titania, and zirconia as a support.
- モリブデン、ビスマス、鉄、コバルト、及びイオン半径が0.96Åよりも大きな元素A(ただし、カリウム、セシウム及びルビジウムを除く)を含む、触媒を構成する原料を混合して原料スラリーを得る混合工程と、
得られた該原料スラリーを乾燥して乾燥体を得る乾燥工程と、
得られた該乾燥体を焼成する焼成工程と、
を有し、
前記焼成工程は、前記乾燥体を100℃から200℃まで1時間以上掛けて徐々に昇温する昇温工程を有する、酸化物触媒の製造方法。 A mixing step of mixing a raw material constituting a catalyst containing molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius larger than 0.96 た だ し (excluding potassium, cesium, and rubidium) to obtain a raw slurry ,
A drying step of drying the obtained raw material slurry to obtain a dried product,
A firing step of firing the obtained dried body;
Have
The said baking process is a manufacturing method of an oxide catalyst which has a temperature rising process which heats up the said dry body gradually over 100 hours from 100 degreeC to 200 degreeC. - 前記原料スラリーのpHが8以下である、請求項5に記載の酸化物触媒の製造方法。 The method for producing an oxide catalyst according to claim 5, wherein the pH of the raw slurry is 8 or less.
- 前記焼成工程は、200~300℃の温度で仮焼成して仮焼成体を得る仮焼成工程と、
得られた仮焼成体を300℃以上の温度で本焼成して触媒を得る本焼成工程と、
を有する、請求項5又は6に記載の酸化物触媒の製造方法。 The calcining step includes calcining at a temperature of 200 to 300 ° C. to obtain a calcined product,
A main firing step of subjecting the obtained temporary fired body to a main firing at a temperature of 300 ° C. or higher to obtain a catalyst;
The manufacturing method of the oxide catalyst of Claim 5 or 6 which has these. - 請求項1~4のいずれか1項に記載の酸化物触媒を用いて、オレフィン及び/又はアルコールを酸化して不飽和アルデヒドを得る不飽和アルデヒド製造工程を有する、不飽和アルデヒドの製造方法。 A method for producing an unsaturated aldehyde, comprising an unsaturated aldehyde producing step of obtaining an unsaturated aldehyde by oxidizing an olefin and / or alcohol using the oxide catalyst according to any one of claims 1 to 4.
- 前記オレフィン及び/又は前記アルコールが、プロピレン、イソブチレン、プロパノール、イソプロパノール、イソブタノール、及びt-ブチルアルコールからなる群より選ばれる少なくとも1種である、請求項8に記載の不飽和アルデヒドの製造方法。 The method for producing an unsaturated aldehyde according to claim 8, wherein the olefin and / or the alcohol is at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.
- 前記不飽和アルデヒド製造工程において、流動層反応器中で、前記オレフィン及び/又は前記アルコールと、酸素源と、を気相接触酸化反応させ、前記流動層反応器から前記不飽和アルデヒドを含む生成ガスを流出させる流出工程を有する、請求項8又は9に記載の不飽和アルデヒドの製造方法。 In the unsaturated aldehyde production process, in the fluidized bed reactor, the olefin and / or the alcohol and the oxygen source are subjected to a gas phase catalytic oxidation reaction, and the product gas containing the unsaturated aldehyde from the fluidized bed reactor. The manufacturing method of the unsaturated aldehyde of Claim 8 or 9 which has the outflow process which makes an outflow flow.
- 前記気相接触酸化反応の反応温度が400~500℃であり、
前記流動層反応器から流出する前記生成ガス中の酸素濃度が0.03~0.5体積%である、
請求項8~10のいずれか1項に記載の不飽和アルデヒドの製造方法。 The reaction temperature of the gas phase catalytic oxidation reaction is 400 to 500 ° C .;
The oxygen concentration in the product gas flowing out of the fluidized bed reactor is 0.03 to 0.5% by volume,
The method for producing an unsaturated aldehyde according to any one of claims 8 to 10. - 請求項1~4のいずれか1項に記載の酸化物触媒を用いて、炭素数4以上のモノオレフィンを酸化してジオレフィンを得るジオレフィン製造工程を有する、ジオレフィンの製造方法。 A method for producing a diolefin, comprising a diolefin production step of obtaining a diolefin by oxidizing a monoolefin having 4 or more carbon atoms using the oxide catalyst according to any one of claims 1 to 4.
- 請求項1~4のいずれか1項に記載の酸化物触媒を用いて、流動層反応器内で、プロピレン、イソブチレン、プロパノール、イソプロパノール、イソブタノール、及びt-ブチルアルコールからなる群より選ばれる1種以上と、分子状酸素と、アンモニアと、を反応させて不飽和ニトリルを得る不飽和ニトリル製造工程を有する、不飽和ニトリルの製造方法。 1 selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol in the fluidized bed reactor using the oxide catalyst according to any one of claims 1 to 4. A method for producing an unsaturated nitrile, comprising the step of producing an unsaturated nitrile by reacting a seed or more, molecular oxygen, and ammonia to obtain an unsaturated nitrile.
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Also Published As
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CN104661747B (en) | 2017-02-15 |
RU2015109709A (en) | 2016-11-20 |
EP2902106A4 (en) | 2015-10-21 |
MY177749A (en) | 2020-09-23 |
BR112015006012A2 (en) | 2017-07-04 |
BR112015006012B1 (en) | 2020-11-10 |
RU2615762C2 (en) | 2017-04-11 |
CN104661747A (en) | 2015-05-27 |
US20150238939A1 (en) | 2015-08-27 |
JPWO2014051090A1 (en) | 2016-08-25 |
US9364817B2 (en) | 2016-06-14 |
KR101741930B1 (en) | 2017-05-30 |
KR20150046224A (en) | 2015-04-29 |
SG11201501592QA (en) | 2015-05-28 |
TWI511784B (en) | 2015-12-11 |
EP2902106A1 (en) | 2015-08-05 |
TW201420185A (en) | 2014-06-01 |
JP5908595B2 (en) | 2016-04-26 |
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